JPH07114274A - Color image forming method and device used therein - Google Patents

Abstract

PURPOSE:To easily and stably obtain a high-definition and high-quality image without color slurring by transferring a toner image on a primary receptor where a peelable transfer layer is provided and then transferring it together with the transfer layer on a final material to be transferred. CONSTITUTION:The toner image 3 of one or more colors is formed on an electrophotographic photoreceptor 11 consisting of at least a supporting body 1 and a photoreceptive layer 2 by using an ordinary electrophotographic process, and transferred on the transfer layer 22 provided on the primary receptor 20. Thus, the toner image 3 on the photoreceptor is sufficiently peeled from the photoreceptor 11 by utilizing a resin layer being the transfer layer, and easily and perfectly transferred on the transfer layer 22. Furthermore, the toner image 3 is transferred to the final material to be transferred 30 together with the transfer layer 22, so that a color copied substance is obtained. Thus, the high- definition and high-quality color image with little color slurring is easily and stably obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color image forming method using electrophotography applicable to the fields of color copying machines, color printers, color proofers, color checkers and the like, and an apparatus used therefor.

[0002]

2. Description of the Related Art Toners of a plurality of colors are sequentially overlaid on an electrophotographic photosensitive member surface using a developer for electrostatic photography to develop a color image to form a color image, which is then transferred at a time to a transfer material such as printing paper. By doing so, a method of producing a color image printed matter, a color image copy or a color proof (proof for printing) is known. Such a developing method includes a so-called dry developing method and a wet developing method. The color image obtained by using the wet development method is preferable because there is no color shift of each color and a high-resolution color image can be obtained as compared with the case of dry toner.
It is extremely difficult to completely transfer the wet toner image directly from the surface of the photoconductor to the actual paper.

In order to solve this problem, Japanese Patent Laid-Open No. 2-272
Japanese Patent Publication No. 469 discloses a technique in which a non-aqueous solvent is supplied between a material to be transferred and a photoconductor at the time of transfer, and then electrostatically transferred. In addition, JP-A-2-115865 and 2-
In JP-A-115866, after a transparent film is laminated on the surface of a photoconductor in advance, a wet toner image is formed on the film by an electrophotographic process, and then the film is peeled from the photoconductor and attached to plain paper to form an image. A method of transferring is disclosed. However, in this case, the film to be laminated is 9
Although a thickness of μm is suitable, the production and handling of a film having such a thickness are extremely troublesome, and it is necessary to take measures separately for that purpose.

Further, Japanese Patent Publication No. 2-43185 discloses that
A method is disclosed in which a transparent electrophotographic photosensitive member is exposed from the rear side to form an overlapping color separation image on a dielectric support, and the whole support is transferred onto a transfer material. In this method, light is exposed from the transparent support side of the photoreceptor, and the conductive layer must be transparent, which is disadvantageous in terms of cost.

On the other hand, Japanese Unexamined Patent Publication Nos. 1-112264 and 1-
No. 281464 and No. 3-11347, in an electrophotographic transfer method using a so-called dry development method, a peelable transfer layer is provided in advance on the surface of a photoconductor, and a toner image is formed thereon. Proposals have been made to transfer the entire transfer layer onto the paper. However, in these techniques, when the photoreceptor is repeatedly used, a special operation is required at the time of transfer, and it is difficult to form the transfer layer. Further, in the method of using the photoconductor on which the transfer layer (or the peeling layer) is formed in advance, the photoconductor must be thrown away, and the disadvantage in terms of cost cannot be avoided.

On the other hand, Japanese Patent Laid-Open No. 2-264280 describes a method of transferring a toner image on a photosensitive layer to a highly smooth primary intermediate transfer medium and then transferring it onto a final transfer material.
Further, JP-A-3-243973 and JP-A-4-9087 propose a method of obtaining a good final color image even with a wet toner by using a special transfer medium.

[0007]

In these methods, it is said that the toner image can be clearly transferred without being affected by the surface unevenness of the material to be transferred, but the toner image can be directly transferred to the primary intermediate transfer medium, Since the image is transferred onto the final transfer material, the resulting color image has a missing toner image or uneven image density, and in particular, fine image defects such as fine lines and fine characters are observed. Further, the toner image remains on the surface of the photoconductor or the intermediate medium after the transfer of the toner image. This means that when the photoconductor or the intermediate medium is repeatedly used, it becomes necessary to clean the surface, and further, the setting of the apparatus for that purpose and the damage to the surface of the photoconductor or the intermediate medium due to the cleaning become a problem. come. As described above, in the conventional color image forming method using an intermediate transfer medium, a sufficiently satisfactory color image cannot be obtained, and the properties of the intermediate medium change when repeatedly used, and stable performance is maintained for a long period of time. However, there are various problems such as that it is difficult to perform, a disposable member is generated to maintain the performance, and it is necessary to use a special transfer medium.

The present invention solves the problems of the above-described conventionally known electrophotographic transfer image forming methods. An object of the present invention is to provide a toner image with excellent transferability, without color shift, to obtain a high-definition, high-quality color image easily and stably, and to obtain an excellent color image without selecting a final transfer material. To provide a reproducible novel electrophotographic color image forming method using a transfer layer as an intermediate medium (primary receptor) and an apparatus used therefor. Further, another object of the present invention is to use a transfer device having a simple structure in the electrophotographic apparatus to form a transfer layer on the primary receptor in the electrophotographic apparatus each time, thereby making it possible to reduce the running cost. In addition, the release property of the surface of the photoconductor and the surface of the primary receptor is well controlled and maintained, and the interface between the photoconductor and the toner image part and the interface between the transfer layer and the primary receptor are clearly formed and maintained, so that the toner image and the transfer image are transferred. It is a further object to facilitate the formation and peeling of layers.

[0009]

SUMMARY OF THE INVENTION The primary object of the present invention is to provide a peelable transfer layer by forming a toner image of one or more colors on an electrophotographic photosensitive member having a releasable surface by an electrophotographic process. It has been found to be achieved by a color image forming method characterized in that the toner image is transferred onto a receptor and then the toner image on the primary receptor is transferred with the transfer layer to a final transfer material.

The color image forming method of the present invention uses an ordinary electrophotographic process on an electrophotographic photosensitive member 11 comprising at least a support 1 and a photosensitive layer 2, as shown in FIG. To form a toner image 3 of one or more colors, and the toner image 3 is transferred onto a transfer layer 22 provided on the primary receptor 20. Further, the toner image 3 is transferred to the final transfer material 30 together with the transfer layer 22 to form a color copy.

In the present invention, the toner image formed on the photoreceptor is transferred onto the primary receptor having a transfer layer.
The toner image on the photoconductor is sufficiently peeled from the photoconductor by using the resin layer, which is the transfer layer, and can be easily and completely transferred to the transfer layer. Further, since the color image is transferred onto the transfer layer and then transferred together with the transfer layer to the final transfer target material, a color image with little color shift and high definition and high image quality can be easily and stably obtained. Further, a transfer device having a simple structure is sufficient, and a color image can be formed regardless of the final transfer material.

The peelable transfer layer is preferably formed on the primary receptor by at least one of a hot melt coating method, an electrodeposition coating method and a transfer method. This makes it possible to form a transfer layer on the primary receptor in the electrophotographic process apparatus, and enables repeated use and continuous operation of the primary receptor.

Further, the surface of the electrophotographic photosensitive member to be used in the present invention has an adhesive force of not more than 100 gram · force (g · f) according to “Test method for adhesive tape / adhesive sheet” of JIS Z0237-1980, more preferably 50 g · f or less, particularly preferably 3
It is preferably 0 g · f or less, and the adhesive force on the surface of the primary receptor is larger than the adhesive force on the surface of the photoreceptor, preferably 10 g · f or more, and particularly preferably 50 g · f or more. The maximum adhesion of the primary receptor surface is 250g.
f, and particularly preferably 200 g · f or less. By adjusting the adhesive force in this way, the releasability of the photoconductor and the transfer layer can be satisfactorily exhibited, and the toner image is transferred from the photoconductor to the primary receptor and the transfer layer from the primary receptor to the final transfer material. It is possible to easily transfer the toner image for each toner. If further added, the adhesive force between the primary receptor surface and the final transferred material surface is preferably such that at least the former has a smaller adhesive force than the latter.

The adhesive strength is measured according to JIS Z0237-1980 "Adhesive tape / adhesive sheet test method" described in 18 of 8.3.1.
Follow the 0-degree peeling method with the following modifications. As the "test plate", an electrophotographic photoreceptor on which a toner image is to be formed or a primary receptor on which a transfer layer is to be formed is used. As the “test piece”, an adhesive tape having a width of 6 mm and manufactured according to JIS C 2338-1984 is used. Peel at a speed of 120 mm / min using a constant speed tension type tensile tester. That is, with the adhesive surface of the test piece facing down, the roller is reciprocated once over the test piece at a speed of about 300 mm / min to the test plate. During 20 to 40 minutes after crimping, using a constant speed tension type tensile tester, after peeling off about 25 mm, 120
Peel off at a speed of mm / min. The force is read every time it is peeled off by 20 mm, and a total of 4 times is read. The test is performed on three test pieces, and an average value of twelve pieces measured from the three test pieces is obtained, and the average value is proportionally converted per 10 mm width. Also in the case of measuring the adhesive force of the final transfer material, this is used as a test plate and is carried out in the same manner as above.

Further, in the present invention, a peelable surface is obtained by adopting a simple method of adsorbing or adhering the compound (S) containing at least a fluorine atom and / or a silicon atom on the surface of the electrophotographic photosensitive member. It can be a photoreceptor. In this way, by adopting the means for imparting releasability to the photoconductor, a releasable surface can be easily provided by using an ordinary electrophotographic photoconductor without considering the releasability of the surface of the electrophotographic photoconductor itself. A photoreceptor can be obtained.

Further, the releasability (adhesive force) of the surface of the primary receptor can be adjusted by adsorbing or adhering the above compound (S) on the surface of the primary receptor.
Further, the formation of the transfer layer on the primary receptor is carried out by using the organic solvent 1.
By carrying out electrodeposition coating of a resin particle dispersion for electrodeposition containing at least one compound (S) containing a fluorine atom and / or a silicon atom which dissolves at least 0.01 g in 0 liter, The peelability can be adjusted and the transfer layer can be formed at the same time.

On the other hand, the present invention provides a means for forming a toner image of at least one color on an electrophotographic photosensitive member having a peeling property by an electrophotographic process, a means for providing a peelable transfer layer on the primary receptor, and a means for forming the primary receptor. And a means for transferring the toner image and a means for transferring the toner image from the primary receptor to the final transfer material together with the transfer layer. The color image forming apparatus further comprises a fluorine atom and / or a fluorine atom on the surface of the electrophotographic photosensitive member and / or the primary receptor depending on the degree of surface releasability of the electrophotographic photosensitive member to be used and the degree of surface adhesion of the primary receptor. It may have a means for supplying the compound (S) containing at least a silicon atom.

Next, the electrophotographic photosensitive member used in the present invention will be described. As the electrophotographic photoreceptor, any conventionally known one can be used. What is important is that the surface of the photoreceptor be releasable prior to the toner development process so that the toner image formed on the photoreceptor can be easily stripped. In the present invention, as described above,
The adhesive strength of the surface of the photoreceptor before toner image formation according to JIS Z0237-1980 "Adhesive tape / adhesive sheet test method" is
100g ・ f or less, more preferably 50g ・ f or less, especially 30g
-It is preferable that it is not more than f. To obtain a photoreceptor having a releasable surface, specifically, a method using a photoreceptor having a releasable surface in advance, or a release compound (S) is adsorbed or attached to the surface of a commonly used electrophotographic photoreceptor A method of imparting releasability to the surface of the photoreceptor by doing so is mentioned.

Examples of the former photosensitive body having a releasable surface include a photosensitive body using amorphous silicon as a photoconductor, and an electrophotographic photosensitive body containing at least one of a fluorine atom and a silicon atom near the surface thereof. Examples thereof include a polymer containing a polymer component (containing a fluorine atom and / or a silicon atom). Here, the vicinity of the surface of the electrophotographic photosensitive member means the uppermost layer of the photosensitive member, and includes the overcoat layer and / or the uppermost photoconductive layer provided on the photoconductive layer. That is, an overcoat layer is provided as the uppermost layer of the photoconductor having a photoconductive layer, and the polymer is added to the overcoat layer to impart releasability, or a photoconductive layer (photoconductive single layer and photoconductive layer The above-mentioned polymer may be contained in the uppermost layer of any of the body laminates), and the surface thereof may be modified to a state in which releasability is exhibited.

In order to impart releasability to the overcoat layer or the uppermost photoconductive layer, a polymer containing a silicon atom and / or a fluorine atom is used as a binder resin for the layer, or a silicon atom and / or a fluorine atom is used. There is a method of using a small amount of a block copolymer containing a polymer segment composed of a fluorine atom-containing polymer component (hereinafter referred to as a surface unevenly distributed copolymer) together with another binder resin. Further, such a resin containing silicon and / or fluorine atoms may be used in the form of particles. Among them, when the overcoat layer is provided, the method of using the surface unevenly distributed block copolymer in combination is preferable because the adhesion between the photoconductor layer and the overcoat layer can be sufficiently maintained. The surface unevenly distributed copolymer can be used in combination with another binder resin in a proportion of usually 0.1 to 20 parts by weight based on 100 parts by weight of the total composition of the overcoat layer.

As such an overcoat layer, specifically, in a PPC photoreceptor using a dry toner,
A protective layer used for providing a surface layer on the photoconductor to protect the photoconductor is known as one means for maintaining durability of the photoconductor surface against repeated use. For example, a technique relating to a protective layer using a silicone block copolymer is disclosed in Japanese Patent Laid-Open No. 9535/1986.
No. 8, JP-A-55-83049, JP-A-62-879.
71, JP-A 61-189559, JP-A 62-7.
5461, JP-A-62-75461, JP-A-62-
Examples thereof include those described in JP-A No. 139556, JP-A No. 62-139557, JP-A No. 62-208055, and the like. Further, as the protective layer using a fluorine-based block copolymer, there are disclosed in JP-A-61-116362, JP-A-61-117563, JP-A-61-270768,
Examples thereof include those described in JP-A-62-14657 and the like. Further, examples of the protective layer in which a resin containing a fluorine atom-containing polymer component is used in the form of particles include those described in JP-A-63-249152 and JP-A-63-221355. .

Further, the method of modifying the surface of the uppermost photoconductive layer to a state of exhibiting releasability is a method of using a so-called dispersion type photoconductor in which at least a photoconductor and a binder resin are used. Effectively applied. That is, in the layer constituting the uppermost layer of the photoconductive layer, a resin of a block copolymer containing a polymer segment containing a polymer component containing a fluorine atom and / or a silicon atom in a block, and a fluorine atom and / or
Alternatively, by coexisting at least one of the resin particles containing the silicon atom-containing polymer component, these materials are concentrated / migrated to the surface and unevenly distributed, so that the surface can be modified to a peelable surface. As the copolymer and the resin particles, the same ones as described in JP-A-5-197169 can be mentioned.

Further, in order to strengthen the uneven distribution of the surface, as a binder resin for the overcoat layer and the photoconductive layer, a polymer segment containing a fluorine atom and / or a silicon atom, and heat and / or photocuring are used. It is possible to use a block copolymer obtained by bonding at least one type of polymer segment containing a functional group-containing component in blocks. Examples of the polymer segment containing such a heat- and / or photo-curable group-containing component include the same as those described in JP-A-5-197169. Further, a light and / or thermosetting resin may be used together with a resin containing a fluorine atom and / or a silicon atom.

In the electrophotographic photosensitive member having a peelable surface in advance, in addition to the electrophotographic photosensitive member mainly containing amorphous silicon, the fluorine atom of the present invention effective for modifying the photosensitive member surface by the above-mentioned method. And / or the polymer containing the polymer component containing a silicon atom is composed of resin {hereinafter referred to as resin (P)} or resin particles {hereinafter referred to as resin particle (L)}.

When the polymer is a random copolymer, the content of the polymer component containing a fluorine atom and / or a silicon atom is preferably at least 60% by weight, more preferably at least 60% by weight based on the total polymer component. Is 80% by weight or more. More preferably, a polymer segment (α) containing 50% by weight or more of a polymer component containing a fluorine atom and / or a silicon atom and a polymer segment containing 0 to 20% by weight of a polymer component containing a fluorine and / or silicon atom. It is a block copolymer in which united segments (β) are linked by blocks. More preferably, at least one photo- and / or thermosetting functional group is contained in the segment (β) in the block copolymer.
It is a block copolymer containing at least one polymer component containing a seed. In these block copolymers, the segment (β) preferably contains no fluorine atom and / or silicon atom-containing polymer component.

By using a block copolymer (surface unevenly distributed copolymer) containing the polymer segment (α) and the segment (β) in the above-mentioned polymer, the surface is exfoliated as compared with the random copolymer. The property is improved, and the peelability is maintained. That is, when a coating film is formed by coexisting a small amount of a resin (P) and / or resin particles (L) containing a fluorine atom and / or a silicon atom, the resin (P) can be formed by the end of the drying step after coating. The resin particles (L) are easily transferred to and concentrated on the surface of the film, and the surface of the film is modified so as to exhibit releasability. As described above, when the polymer segment (α) containing a fluorine atom and / or a silicon atom is blocked, the other polymer segment (β) has a compatibility with the binder resin for film formation. Since they are good, they sufficiently interact with each other, and even during the formation of a toner image and the pressure contact of the transfer layer, these resins suppress or eliminate the transfer to the toner image or the transfer layer, and The interface between the transfer layer and the electrophotographic photosensitive member can be clearly formed and maintained (that is, the anchor effect). By using a polymer having a light and / or thermosetting group in the segment (β) of the block copolymer to crosslink between the polymers at the time of film formation, the photoreceptor and the toner image or the transfer layer can be further formed. The effect of clearly maintaining the peeling property of the interface is exhibited.

The polymer is the resin particles (L) as described above.
May be used in the form of. Preferred resin particles (L)
Are resin particles dispersed in a non-aqueous solvent. Such resin particles include a polymer component containing a fluorine atom and / or a silicon atom-containing polymer component, which is insoluble in a non-aqueous solvent, and a polymer component containing a fluorine atom and / or a silicon atom. Even if it is 20% or less, a polymer segment (β) soluble in a non-aqueous solvent is bonded. In the case of resin particles, due to the action of the insolubilized polymer portion, migration and concentration to the surface are performed, and further, the polymer segment (β) soluble in the non-aqueous solvent bound to the particles is In the same manner as in (1), it interacts with the binder resin and acts as an anchor effect. Further, by containing a light and / or thermosetting group in the polymer or in the binder resin, migration to the toner image or the transfer layer is eliminated.

The polymer component containing a substituent containing a fluorine atom and / or a silicon atom contained in the resin (P) and / or the resin particle (L) has a polymer main chain of the polymer as the substituent. And those contained as a substituent on the side chain of the polymer. Examples of the substituent containing a fluorine atom include the following monovalent or divalent organic residues.

[0029]

[Chemical 1]

[0030]

[Chemical 2]

Examples of the substituent containing a silicon atom include the following monovalent or divalent organic residues.

[0032]

[Chemical 3]

However, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R
^{15's, which} may be the same or different, each represents an optionally substituted hydrocarbon group or an -OR ¹⁶ group (R ¹⁶ represents an optionally substituted hydrocarbon group). As the hydrocarbon group represented by R ^{11 to} R ¹⁶ , specifically, an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group,
Decyl group, dodecyl group, hexadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2,2-trifluoroethyl group, 2-cyanoethyl group, 3,3,3-trifluoropropylethyl group, 2-methoxy Ethyl group, 3-
Bromopropyl group, 2-methoxycarbonylethyl group,
2,2,2,2 ', 2', 2'-hexafluoroisopropyl group, etc.), an alkenyl group having 4 to 18 carbon atoms which may be substituted (for example, 2-methyl-1-propenyl, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), substituted with 7 to 12 carbon atoms Aralkyl groups (eg benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group) Group, dimethoxybenzyl group, etc.), an alicyclic group having 5 to 8 carbon atoms which may be substituted (eg, cyclohexyl group,
2-cyclohexyl group, 2-cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms (eg, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, Octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonyl Phenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group and the like).

Further, the organic residue containing a fluorine atom and / or a silicon atom may be constituted in combination, in which case it may be directly bonded or further via another linking group. It may be combined. Specific examples of the group to be linked include a divalent organic residue, -O-, -S
^{-, - N (d 1)} -, - CO -, - SO -, - SO 2 -,
-COO-, -OCO-, -CONHCO-, -NHC
^{ONH -, - CON (d 1} ) -, - SO 2 N (d 1) - may be interposed selected linking groups from such a divalent aliphatic group or a divalent aromatic group, or they Represents an organic residue composed of a combination of divalent residues of here,
d ¹ has the same meaning as R ¹¹ .

Examples of the divalent aliphatic group include the groups shown below.

[0036]

[Chemical 4]

Here, e ¹ and e ² may be the same as or different from each other, and each is a hydrogen atom or a halogen atom (for example,
(Chlorine atom, bromine atom, etc.) or alkyl group having 1 to 12 carbon atoms (for example, methyl group, ethyl group, propyl group, chloromethyl group, bromomethyl group, butyl group, hexyl group, octyl group, nonyl group, decyl group, etc.) Represents Q is -O
-, - S- or -N (d ²⁾ - represents, d ² is 1 to the number of carbon atoms
4 represents an alkyl group of 4, —CH ₂ Cl or —CH ₂ Br.

Examples of the divalent aromatic group include a benzene ring group, a naphthalene ring group and a 5- or 6-membered heterocyclic group (as a hetero atom constituting the hetero ring, selected from an oxygen atom, a sulfur atom and a nitrogen atom). Containing at least one hetero atom). These aromatic groups may have a substituent, for example, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group). , A butyl group, a hexyl group, an octyl group, etc.) and an alkoxy group having 1 to 6 carbon atoms (eg, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.) can be given as examples of the substituent.
Examples of the heterocyclic group include a furan ring, a thiophene ring, a pyridine ring, a piperazine ring, a tetrahydrofuran ring, a pyrrole ring, a tetrahydropyran ring, and a 1,3-oxazoline ring.

Specific examples of the repeating unit having a substituent containing a fluorine atom and / or a silicon atom as described above are shown below. However, the scope of the present invention is not limited to these. In each of the following examples (F-1) to (F-32), R _f represents any of the groups (1) to (11) shown below, and b represents a hydrogen atom or a methyl group.

[0040]

[Chemical 5]

However, in the above (1) to (11), R _f ′ represents the group represented by the above (1) to (8), n represents an integer of 1 to 18, and m represents 1 to 18. An integer is shown, and 1 is an integer of 1 to 5.

[0042]

[Chemical 6]

[0043]

[Chemical 7]

[0044]

[Chemical 8]

[0045]

[Chemical 9]

[0046]

[Chemical 10]

In the resin (P) and the resin particles (L),
In the case of a so-called surface uneven distribution type copolymer, in the segment (α) containing a silicon atom and / or a polymer component containing a silicon atom, the polymer component is at least in the total amount of the entire segment (α). It is 50% by weight, preferably 70% by weight or more, more preferably 80% by weight or more. Further, in the segment (β), the content of the polymer component containing a fluorine atom and / or a silicon atom is 20% by weight or less, and preferably 0% by weight, of the total amount of the segment (β).

The weight ratio of the segment (α) to the segment (β) is 1 to 95: 5 to 99, preferably 5 to 90: 1.
0 to 95. If the amount is out of this range, the concentration effect on the surface of the uppermost layer of the photoconductive layer and the anchor effect of both the resin (P) and the resin particles (L) decrease. The weight average molecular weight of the resin (P) is preferably 5 × 10 ³ to 1 × 10 ⁶ , and more preferably 1 × 10 ^{4 to} 5 × 10 ⁵ . The weight average molecular weight of the segment (α) in the resin (P) is 1 × 10 ^3.
The above is preferable. The average particle diameter of the resin particles (L) is preferably 0.001 to 1 μm, more preferably 0.05 to 0.5 μm.

Preferred embodiments of the so-called surface unevenly distributed copolymer in the resin (P) will be described below. Any one may be used as long as the polymer component containing a fluorine atom and / or a silicon atom in the resin (P) is composed of a block. Here, being composed of blocks means that fluorine atoms and /
Alternatively, it means that the polymer has a polymer segment (α) containing 50% by weight or more of a silicon atom in the polymer. For example, an AB block, an ABAA block, and a B block as shown below. -AB type block, a graft type block, a star type block etc. are mentioned.

[0050]

[Chemical 11]

These various block copolymers can be synthesized by a conventionally known polymerization method. For example,
WJBurlant, ASHoffman `` Block and Graft polymer
s ”(1986, Reuhold), RJ Cevesa“ Block and Graft
Copolymers "(1962, Butterworths), DC Allpor
t, WH James “Block Copolymers” (1972, Applied
Sci), A. Noshay, JEMc Grath "Block Copolymers"
(1977, Academicis Press.), G.Huvterg, DJ Wilso
n, G.Riess, NATO ASIser.SerE. 1985 , 149, V.Perce
s, Applide. Polymer Sci. 285, 95 (1985) and other books and reviews.

For example, TEHogeu-Esch can be used for the ionic polymerization reaction using an organometallic compound (eg, alkyllithium, lithium diisopropylamide, alkali metal alcoholates, alkylmagnesium halides, alkylaluminum halides) as a polymerization initiator. ,
J. Smid "Recent Advances in Anion Polymerization"
(1987, Elsevier New York), Yoshio Okamoto, Polymer, 3
8 , 912 (1989), Sawamoto Mitsuo, Polymer, 38 , 1018 (1989), Narita Tadashi, Polymer, 37 , 252 (1988), BC Anderson et a
l., Macromolecules 14 , 1601 (1981), S. Aoshima, TH
igashimura, Macromolecules 22 , 1009 (1989) and the like.

Regarding the ionic polymerization reaction with hydrogen iodide / iodine system, etc., see T. Higashimura at al., Macrom.
ol. Chem., Macromol. Symp ., 13/14, 457 (1988), Higashimura Satoshinobe, Mitsuo Sawamoto, by Kobunshi Ronbunshu 46, 189 (1989) and the like. For group transfer polymerization reaction, see DY
Sogah et al., Macromolecules, 20 , 1473 (1987), OW
Webster, DYSogah, Polymer, 36 , 808 (1987), MTRee
tg et al., Angew. Chem. Int. Ed. Eugl. 25 , 9108 (198
6), JP-A-63-97609 and the like.

Regarding the living polymerization reaction using the metalloporphyrin complex, T. Yasuda, T. Aida, S. Inoue, Macro.
molecules, 17 , 2217 (1984), M. Kuroki, T. Aida, S. Ino
ue, T. Ann. Chem. Soc. 109 , 4737 (1987), M. Kuroki et
al., Macromolecules, 21 , 3115 (1988), M. Kuroki, I.
Inoue, Synthetic Organic Chemistry, 47 , 1017 (1989) and the like.

Further, regarding ring-opening polymerization reaction of a cyclic compound, S. Kobayasi, T. Saegusa "Ring Opening Polymeri"
zation '' (1984, Applied Scence Publishers Ltd.),
W. Seeliger et al., Angew. Chem. Int. Ed. Engl.
5 , 875 (1966), S. Kobayashi et al., Poly. Bull. 13 ,
447 (1985), Y. Chujo et al., Macromolecules, 22 , 107.
4 (1989). Furthermore, for the living photopolymerization reaction using a dithiocarbamate compound or a xanthate compound as an initiator, Takayuki Otsu, a polymer,
37 , 248 (1988), Shunichi Hinomori, Ryuichi Otsu, Polym. Rep. Ja
p. 37 , 3508 (1988), JP-A-64-111, JP-A-64
-26619, M. Niwa, Macromolecules, 189 , 2187.
(1988).

[0056] On the other hand, a method of synthesizing a block copolymer by radical polymerization reaction to polymeric initiator containing an azo group or a peroxide group, Ueda Akirato, polymeric Ronbunshu 33,
931 (1976), Akira Ueda, Osaka City Research Institute Report 84 (198)
9), O. Nuyken et al., Macromol. Chem., Rapid. Comm.
un. 9 , 671 (1988), Ryohei Oda "Science and Industry" 61 , 43 (19)
87) etc.

Regarding the synthesis of the graft type block copolymer, in addition to the above-mentioned books and reviews, Fumio Ide “Graft polymerization and its applications” (1977, Polymer Society of Japan), Polymer Society, edited by “Polymer”・ Alloy ”(1981, Tokyo Kagaku Dojin). For example, a method of grafting a polymer chain with a polymerization initiator, chemical actinic rays (radiation, electron beam, etc.), mechanochemical reaction in mechanical application, etc., polymer chains and functional groups of polymer chains There is known a method of grafting by utilizing a chemical bond (so-called interpolymer reaction), a method of polymerizing a macromonomer and grafting. As a method of grafting using a polymer, specifically, T. Shota et al., J. Appl. Polym. Sc
i. 13 , 2447 (1969), WHBuck, Rubber Chemistry and
Technology, 50 , 109 (1976), Takeshi Endo, Tsutomu Uezawa, Journal of Japan Adhesion Society, 24 , 323 (1988), Takeshi Endo, ibid. 25 , 409 (198)
9) etc.

Further, as a method of carrying out a polymerization reaction and grafting using a macromonomer, specifically, P. Dreyfuss
& RPQuirk, Encycl. Polym. Sci. Eng., 7 , 551 (19
87), PFRempp, E.Franta, Adv. Polym. Sci., 58 , 1
(1984), V. Percec, Appl. Poly. Sci., 285, 95 (198
4), R. Asami, M. Takari, Macromol. Chem. Suppl., 1
2 , 163 (1985), P. Rempp. Et al., Macromol. Chem. Supp.
L., 8 , 3 (1985), Yusuke Kawakami, Chemical Industry, 38 , 56 (198)
7), Yuya Yamashita, Polymer, 31 , 988 (1982), Shiro Kobayashi, Polymer, 30 , 625 (1981), Toshinobu Higashimura, Journal of Japan Adhesion Society, 1
8 , 536 (1982), Koichi Ito, Polymer processing, 35 , 262 (198
6), Kishiro Higashi, Takashi Tsuda, Functional Materials, 1987 , No.10, 5,
Edited by Yuya Yamashita, "Chemistry and Industry of Macromonomers" (1989
"PC Design Co., Ltd.", edited by Takeshi Endo, "Molecular Design of New Functional Polymers", Chapter 4 (1991, CMC Co., Ltd.),
Y. Yamashita et al., Polym. Bull. 5 , 361 (1981) and the like.

The synthesis method of the star type block copolymer is as follows:
For example MT Reetz, Angew. Chem. Int. Ed. Engl., 2
7 , 1373 (1988), M. Sgwarc `` Carbanions, Living Polyme.
rs and Electron Transfer Prodesses '' (1968, Wiley.
New York), B. Gordon et al., Polym. Bull. 11 , 349 (1
984), RBBates et al., J. Org. Chem. 44 , 3800 (197
9), Y. Sogah, ACS Polym. Rapr. 1988 , No. 2, 3, J.
W. Mays. Polym. Bull. 23 , 247 (1990), IMKhan et a
L., Macromolecules, 21 , 2684 (1988), A. Morikawa, Ma.
cromolecules, 24 , 3469 (1991), Akira Ueda, Toru Nagai, Polymer 39 , 202 (1990), T.Otsu, Polym. Bull. 11 , 135 (1984)
Etc. However, the method of synthesizing the block copolymer is not limited to these methods.

Next, a preferred embodiment of the resin particles (L) will be described. As described above, the resin particles (L) are
Preferably, it is composed of a segment (α) containing a fluorine atom and / or a silicon atom which is insoluble in a non-aqueous solvent and a segment (β) containing almost no fluorine atom and / or a silicon atom soluble in the solvent. . Furthermore, the segment (α) part constituting the insoluble part of the resin particles may form a crosslinked structure. A preferable method for producing the resin particles (L) is a non-aqueous dispersion polymerization method.

The non-aqueous solvent used for producing the non-aqueous solvent-based dispersed resin particles may be any organic solvent having a boiling point of 200 ° C. or lower, and may be used alone or in combination of two or more kinds. Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol and benzyl alcohol, ketones such as acetone, methyl ethyl ketone, cyclohexanone and diethyl ketone, ethers such as diethyl ether, tetrahydrofuran and dioxane. , Carboxylic acid esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate, aliphatic hydrocarbons having 6 to 14 carbon atoms such as hexane, octane, decane, dodecane, tridecane, cyclohexane and cyclooctane, benzene, Aromatic hydrocarbons such as toluene, xylene, chlorobenzene,
Examples thereof include halogenated hydrocarbons such as methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, dichloropropane and trichloroethane. However, it is not limited to the above-mentioned compound examples.

By synthesizing dispersed resin particles in these non-aqueous solvent systems by the dispersion polymerization method, the average particle size of the resin particles easily becomes 1 μm or less, and the particle size distribution is very narrow and monodisperse particles. Can be Specifically, the monomer (a) corresponding to the polymer component forming the segment (α) and the monomer (b) corresponding to the polymer component forming the segment (β) (A) is a non-aqueous solvent that dissolves but becomes insoluble when polymerized, using a peroxide (eg, benzoyl peroxide, lauroyl peroxide, etc.), an azobis compound (eg, azobisisobutyronitrile, azobisisovaleronitrile). Etc.), an organic metal compound (eg, butyl lithium, etc.) and the like in the presence of a polymerization initiator. Alternatively, the monomer (a) and the polymer (Pβ) composed of the segment (β) may be polymerized in the same manner as above.

Furthermore, the inside of the insolubilized polymer particles of the resin particles (L) may have a crosslinked structure. Any conventionally known method can be used to form these crosslinked structures. That is, a method of crosslinking a polymer containing a polymer segment (α) with various crosslinking agents or curing agents, and a polymerization reaction is carried out by containing at least a monomer (a) corresponding to the polymer segment (α). At this time, by allowing a polyfunctional monomer or a polyfunctional oligomer containing two or more polymerizable functional groups to coexist,
A method of forming a network structure between molecules and a method of cross-linking the polymer segment (α) with a polymer containing a component containing a reactive group by a polymerization reaction or a polymer reaction. it can.

As the cross-linking agent in the above method, compounds usually used as cross-linking agents can be mentioned. Specifically, "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko.
The compounds described in Taiseisha (1981), "Polymer Data Handbook, Basic Edition" edited by The Polymer Society of Japan, Baifukan (1986), etc. can be used.

For example, organic silane compounds (for example, vinyltrimethoxysilane, vinyltributoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane and other silane coupling agents), polyisocyanate compounds (eg, toluylene diisocyanate, diphenylmethane diisocyanate) Nato, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, high molecular polyisocyanate, etc.), a polyol compound (for example,
1,4-butanediol, polyoxypropylene glycol, polyoxyethylene glycol, 1,1,1-trimethylolpropane, etc., polyamine compounds (for example, ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine). , N-aminoethylpiperazine, modified aliphatic polyamines, etc.), titanate coupling compounds (eg, tetrabutoxy titanate, tetrapropoxy titanate, isopropyl tristearoyl titanate, etc.),
Aluminum coupling compounds (for example, aluminum butyrate, aluminum acetyl acetate, aluminum oxide octate, aluminum tris (acetyl acetate), etc.), polyepoxy group-containing compounds and epoxy resins (for example, "New Epoxy Resin" by Hiroshi Kakiuchi) Do (1985), Kuniyuki Hashimoto, "Epoxy Resin," compounds listed in Nikkan Kogyo Shimbun (1969), melamine resin (for example, Ichiro Miwa, Hideo Matsunaga, "Uria Melamine Resin," Nikkan Kogyo Shimbun Company (1969)
Etc.), poly (meth) acrylate compounds (for example, Shin Okawara, Takeo Saegusa, Toshinobu Higashimura "Oligomer" Kodansha (1976), Eizo Omori "Functional Acrylic Resin" Techno System (Compounds described in (1985)) and the like.

Further, a polyfunctional monomer containing two or more polymerizable functional groups coexisting by the above method [also referred to as polyfunctional monomer (d)] or a polyfunctional oligomer polymerizable functional group. Specifically, CH ₂ ═CHCH
_{2 -, CH 2 = CHCOO-,} CH 2 = CH-, CH 2 = C
_{(CH 3) -COO-, CH (} CH 3) = CHCOO-, CH
_{2 = CHCONH-, CH 2 = C} (CH 3) -CONH-,
_{CH (CH 3) = CHCONH-,} CH 2 = CHOCO-,
_{CH 2 = C (CH 3)} -OCO-, CH 2 = CHCH 2 OCO
_{-, CH 2 = CHNHCO-, CH} 2 = CHCH 2 NHC
_{O-, CH 2 = CHSO 2 -} , CH 2 = CHCO-, CH 2
= CHO-, can be mentioned CH ₂ = CHS-like. Any monomer or oligomer having two or more of the same or different polymerizable functional groups may be used. Specific examples of the monomer having two or more polymerizable functional groups include, for example, a monomer or oligomer having the same polymerizable functional group as a styrene derivative such as divinylbenzene or trivinylbenzene: a polyhydric alcohol (eg,
Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 200, #
400, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc., or polyhydroxyphenols (eg hydroquinone, resorcin, catechol and their Derivatives) methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers: dibasic acids (eg malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid) Etc.) vinyl esters, allyl esters, vinyl amides or allyl amides: polyamines (eg ethylenediamine,
Examples thereof include a condensate of 1,3-propylenediamine, 1,4-butylenediamine, etc.) and a carboxylic acid containing a vinyl group (eg, methacrylic acid, acrylic acid, crotonic acid, allylacetic acid, etc.).

The monomers or oligomers having different polymerizable functional groups include, for example, vinyl group-containing carboxylic acids (eg, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, arylloyl). Propionic acid, itaconiloylacetic acid, itaconiloylpropionic acid, carboxylic acid anhydride, etc.) and alcohol or amine reactants, vinyl group-containing ester derivative or amide derivative (for example, vinyl methacrylate, vinyl acrylate, vinyl itaconate, Allyl methacrylate, allyl acrylate, itaconic acid allyl, methacryloyl vinyl acetate, methacryloyl propionate vinyl, methacryloyl propionate allyl, methacrylic acid vinyloxycarbonyl methyl ester, vinyl acrylate Oxycarbonylmethyloxycarbonyl ethylene ester, N-allyl acrylamide, N-allyl methacrylamide, N-allyl itaconic acid amide, methacryloyl propionic acid allylamide, etc.) or amino alcohols (eg aminoethanol, 1-aminopropanol, 1-aminobutanol) ,
1-aminohexanol, 2-aminobutanol, etc.) and a condensate of a carboxylic acid containing a vinyl group. The amount of the monomer or oligomer having two or more polymerizable functional groups used in the present invention is 10 with respect to the total amount of the monomer (a) and the other monomer coexisting with the monomer (a).
Polymerization is carried out using less than mol%, preferably less than 5 mol% to form a resin.

Further, in the case of forming a chemical bond by the reaction of the reactive groups between the polymers in the above-mentioned method to bridge the polymers, it is carried out in the same manner as the reaction of a normal organic low molecular compound. be able to.

In dispersion polymerization, monodisperse particles having a uniform particle size are obtained, and fine particles of 0.5 μm or less are easily obtained. The method using a monomer is preferable. That is, the synthesis is carried out by polymerizing and granulating the polyfunctional monomer (d) in the presence of the above-mentioned monomer (a), monomer (b) and / or polymer (Pβ). can do.
Furthermore, when the polymer (Pβ) composed of the above-mentioned segment (β) is used, a monomer (a) is attached to a side chain in the polymer main chain of the polymer (Pβ) or one end of the main chain. ), A polymer having a polymerizable double bond group (P
β ′) is preferred.

The polymerizable double bond group may be any as long as it has copolymerizability with the monomer (a) as described above, but a specific example thereof is CH ₂ ═C (p)- COO-, C
_{(CH 3) H = CH-} COO-, CH 2 = C (CH 2 COO
_{H) -COO-, CH 2 = C} (p) -CONH-, CH 2
= C (p) -CONHCOO-, CH 2 = C (p) -C
_{ONHCONH-, C (CH 3) H} = CHCONH-, C
_{H 2 = CHCO-, CH 2 =} CH (CH 2) n -OCO-
(N is 0 or an integer of 1 to 3), CH ₂ = CHO-, CH ₂
═CHC ₆ H ₄ — and the like (where p is —H or —
Represent CH _3).

These polymerizable groups may be directly bonded to the polymer chain or may be bonded via another divalent organic residue. Specific embodiments of these polymers are described in, for example, JP-A 61-43757, JP-A 1-257969,
No. 2-74956, No. 1-282566, No. 2-1
No. 73667, No. 3-15862, No. 4-70669.
No. etc. The total amount of the polymerizable compound is about 5 to 80 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the non-aqueous solvent. The amount of the polymerization initiator is 0.1 to 5% by weight based on the total amount of the polymerizable compounds.
The polymerization temperature is about 30 to 180 ° C, preferably 40 to 120 ° C. The reaction time is preferably 1 to 15 hours.

Next, when a light and / or thermosetting group is contained in the binder resin (P) as a polymer component, or a resin containing a light and / or thermosetting group is used in combination with the resin (P). A case will be described. Light and / or light which may be contained in the resin (P)
Alternatively, examples of the polymer component containing at least one thermosetting group include those described in the above-mentioned known documents, more specifically, those described as the polymerizable functional group, for example. The same thing as is mentioned.

The polymer component containing at least one light and / or curable group contained in these polymers is the polymer segment (β) 100 of the block copolymer.
0.1 to 40 parts by weight, preferably 1 to 3 parts by weight.
0 parts by weight. When the content is within the above range, the curing after the film formation of the photoconductive layer proceeds sufficiently, and the effect of maintaining the film interface between the surface of the electrophotographic photosensitive member and the toner image or the transfer layer is exhibited. Further, the electrophotographic characteristics of the photoconductive layer as the binder resin are not deteriorated, the original reproducibility of the copied image is not deteriorated, and the background fog is not generated in the non-image area. The block copolymer (P) containing these light and / or thermosetting groups is preferably used in an amount of 40% by weight or less based on 100 parts by weight of the total binder resin. If the amount of the resin (P) exceeds 40% by weight, electrophotographic characteristics tend to deteriorate.

Further, the light and / or thermosetting resin (D) may be used in combination with the fluorine atom and / or silicon atom containing resin. The light and / or thermosetting resin (D) may be any conventionally known curable resin, for example,
An example thereof is a resin containing a curable group as described for the block copolymer (P).

These conventionally known binder resins for electrophotographic photosensitive layers are, for example, Ryuji Shibata, Jiro Ishiwatari, Kogaku, No. 17
Vol., Pp. 278 (1968), Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (No.8), Koichi Nakamura, "Techniques of Binders for Recording Materials" Chapter 10, CMC Publishing (1985), Electronic Photographic Society, "Current Symposium on Organic Photoreceptors for Electrophotography"
Proceedings (1985), Hiroshi Komon, "Development and practical use of recent photoconductive materials and photoconductors", Japan Science Information Co., Ltd. (1986), Electrophotographic Society, "Basics and applications of electrophotographic technology" Chapter 5, Corona Corp. (1988), D.Tatt, SCHeidecker, Tappi, 4
9 (No.10), 439 (1966), ESBaltazzi, RGBlanclotte
et al, Phot. Sci. Eng. 16 (No.5), 354 (1972), Nguyen Chan Kay, Isamu Shimizu, Eiichi Inoue, The Journal of The Electrophotographic Society of Japan 18
(No. 2), 22 (1980) and the like, compounds and the like described in reviews.

Specifically, olefin polymers and copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and Derivatives, polymers and copolymers, butadiene-styrene copolymers, isobrene-styrene copolymers, butadiene-unsaturated carboxylic acid ester copolymers, acrylonitrile copolymers, methacrylonitrile copolymers, alkyl vinyl ether copolymers Polymers, acrylic acid ester polymers and copolymers, methacrylic acid ester polymers and copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, itaconic acid diester polymers and copolymers , Maleic anhydride copolymer, acrylamide copolymer, methacrylamide Polymer, hydroxyl group modified silicone resin, polycarbonate resin, ketone resin, polyester resin, silicone resin, amide resin, hydroxyl group and carboxyl group modified polyester resin, butyral resin, polyvinyl acetal resin, cyclized rubber-methacrylic acid ester copolymer, ring Rubber-acrylic acid ester copolymer, a copolymer containing a nitrogen atom-free heterocycle (as a heterocycle, for example, furan ring, tetrahydrofuran ring, thiophene ring, dioxane ring, dioxofuran ring, lactone ring, benzofuran ring, Benzothiophene ring, 1,3-dioxetane ring, etc.), epoxy resin and the like.

More concretely, Takeshi Endo "Refinement of thermosetting polymers" (CMC Co., Ltd., published in 1986), Yuji Harazaki "Handbook of latest binder technology", Chapter II-1 (General Technology Center,
1985), Takayuki Otsu "Synthesis and design of acrylic resin and new application development" (Chubu Business Development Center Publishing Department, 1985), Eizo Omori "Functional acrylic resin" (Technosystem, 1985), etc. The conventionally known resin cited in 1. is used.

As described above, as one embodiment of the pre-peeling photoreceptor of the present invention, the uppermost layer of the photoreceptor, for example, the overcoat layer or the photoconductive layer, is a resin containing a fluorine atom and / or a silicon atom. (P), and optionally other binder resin (B), and further, a light and / or thermosetting resin (D) and / or in order to improve the curing of the film.
Alternatively, it is preferable to allow a small amount of a crosslinking agent to coexist. The amount used is preferably 0.01 to 20% by weight, and more preferably 0.1 to 15% by weight, based on the total amount of the binder resin (B) and the block copolymer (P). With such an amount used, the effect of improving the hardening of the film can be obtained without adversely affecting the electrophotographic characteristics.

Further, it is preferable to use a crosslinking agent in combination,
The compound normally used as a crosslinking agent can be used. Specifically, compounds described in "Crosslinking Agent Handbook" edited by Fuzo Yamashita and Tosuke Kaneko, published by Taisei Co., Ltd. (1981); Can be used. Examples thereof include the compounds described as the cross-linking agent, and further, a monomer having a polyfunctional polymerizable group (for example, vinyl methacrylate, acryl methacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, divinyl succinic acid ester, divinyl). Adipic acid ester, diacrylic succinic acid ester, 2-methylvinyl methacrylate, trimethylolpropane trimethacrylate, divinylbenzene, pentaerythritol polyacrylate and the like).

The uppermost layer of the photoconductive layer is preferably cured after the film formation. The binder resin (B), the block copolymer (P), the curable resin (D) and the cross-linking agent to be provided are preferably used in a combination of functional groups in which polymers are easily chemically bonded. For example, as a polymer reaction due to a combination of functional groups, well-known ones can be mentioned, and specifically, a combination of a functional group of group A and a functional group of group B as shown in the following Table-A is exemplified. . However, it is not limited to this.

[0081]

[Table 1]

In the present invention, a reaction accelerator may be added, if necessary, in order to accelerate the crosslinking reaction in the photosensitive layer film. When the crosslinking reaction is a reaction mode in which a chemical bond between functional groups is formed, for example, organic acids (acetic acid, propionic acid,
Butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc., phenols (phenol, chlorophenol,
Nitrophenol, cyanophenol, bromophenol, naphthol, dichlorophenol, etc.), organometallic compounds (acetylacetonato zirconium salt, acetylacetone zirconium salt, acetylacetocobalt salt,
Dilauric acid dibutoxytin, etc.), dithiocarbamic acid compound (diethyldithiocarbamate, etc.), thiuram disulfide compound (tetramethylthiuram disulfide, etc.), carboxylic acid anhydride (phthalic anhydride, maleic anhydride, succinic anhydride, butylsuccinic anhydride, Three
3 ', 4,4'-tetracarboxylic acid benzophenone dianhydride, trimellitic acid anhydride, etc.) and the like. When the crosslinking reaction is in a polymerizable reaction mode, a polymerization initiator (peroxide, azobis compound, etc. may be mentioned.

The binder resin of the present invention is preferably light-cured and / or heat-cured after the photosensitive layer-formed product is applied. In order to carry out heat curing, for example, the drying conditions are set to be more severe than the conventional drying conditions for producing a photoreceptor. For example, the drying conditions are high temperature and / or long time. Alternatively, it is preferable to further heat-treat after drying the coating solvent. For example 60
Treatment is performed at 5 to 120 ° C. for 5 to 120 minutes. When the above reaction accelerator is used in combination, the treatment can be performed under milder conditions.

As a method of curing the specific functional group in the resin by irradiation with light, a step of irradiating with light of chemically active light may be included. Examples of the chemical actinic rays used in the present invention include visible rays, ultraviolet rays, far ultraviolet rays, electron beams, and X rays.
Any of rays such as rays, γ rays and α rays may be used, but ultraviolet rays are preferable. More preferably, it is a light ray having a wavelength of 310 nm to a wavelength of 500 nm. Generally, a low-pressure, high-pressure or ultra-high-pressure mercury lamp, a halogen lamp or the like is used. The light irradiation treatment can usually be performed sufficiently by irradiation for 10 seconds to 10 minutes from a distance of 5 cm to 50 cm.

Next, in the latter method of obtaining a photoreceptor having a releasable surface, a releasing compound (S) is adsorbed or attached onto the surface of a conventionally known electrophotographic photoreceptor before toner development. Then, a method for obtaining a predetermined adhesive force will be described.

Examples of the releasing compound (S) include compounds containing at least a fluorine atom and / or a silicon atom, and the structure thereof is not particularly limited, and the releasability of the surface of the electrophotographic photosensitive member is improved. Any of low molecular weight compounds, oligomers and polymers may be used as long as they can do so. In particular, in an electrically insulating organic solvent having a relative dielectric constant of 3.5 or less,
The compound (S) containing a fluorine atom and / or a silicon atom, which is soluble in at least 0.01 g in 1.0 liter of the organic solvent, is preferable. In the case of an oligomer or a polymer, the substituent containing a fluorine atom and / or a silicon atom may be incorporated in the main chain of the polymer or may be present as a substituent of the side chain of the polymer. Preferably, the oligomer or polymer includes those containing a repeating unit containing the substituent in a block, and these exhibit particularly excellent adsorbability and releasability on the electrophotographic photoreceptor surface.

These substituents containing a fluorine atom and / or a silicon atom are specifically the same as those described above in relation to the binder resin (P). Specific examples of the compound (S) containing a fluorine atom and / or a silicon atom used in the present invention include “New Edition Surfactant Handbook” edited by Tokiko Yoshida et al., Engineering Book Co., Ltd. (1987).
), Supervised by Takao Karime "Latest, surfactant application technology"
CMC (1990), Kunio Ito, "Silicone Handbook", Nikkan Kogyo Shimbun (1990), Takao Karime, "Special Function Surfactant," CMC (1986)
), AMSchwartz et al "Surface Active Agents an
d Detergents vol.II "and the like, and fluorine-based and / or silicon-based organic compounds. Furthermore, Nobuo Ishikawa “Synthesis and Function of Fluorine Compounds” CMC (1987)
, Hirano, J. Hirano, et al., "Fluorine-Containing Organic Compounds-Synthesis and Applications-", Technical Information Institute (1991), Mitsuo Ishikawa, "Organic Silicon Strategy Materials" Chapter 3, Science Forum (1991) ) And other synthetic methods described in the literature,
The compound (S) of the present invention satisfying the above physical properties can be synthesized.

Specific examples of the polymer component containing a substituent containing a fluorine atom and / or a silicon atom as the oligomer or polymer include the polymer component (F) described in the binder resin (P). Can be mentioned. When the compound (S) of the present invention is a so-called block copolymer, it is sufficient that the polymer component containing a fluorine atom and / or a silicon atom is composed of a block. Here, being composed of blocks means that the polymer has a polymer segment containing 70% by weight or more of a component having a fluorine atom and / or a silicon atom, for example, as described in the resin (P). Similar AB type block, ABAA
Examples thereof include mold blocks, BAB blocks, graft blocks, star blocks and the like. These can be synthesized by the same method as described above.

To adsorb or attach the compound (S) as described above to the surface of the electrophotographic photosensitive member, any conventionally known method may be used. For example, Yuji Harasaki "Coating Engineering" Asakura Shoten Co., Ltd. (published in 1971), Yuji Harazaki "Coating Method" Maki Shoten (published in 1979), Hiroshi Fukada "Practice of Hot Melt Adhesion" Co., Ltd. Polymer Publishing (1979) ) Etc. air doctor coater, blade coater, knife coater, squeeze coater, impregnation coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, spray coater,
Examples include curtain coaters and calendar coaters.

Further, cloth, paper impregnated with the compound (S),
A method in which a felt or the like is brought into close contact with the photoconductor, a method in which a curable resin impregnated with the compound (S) is brought into pressure contact with the photoconductor, and the photoconductor is wetted with a non-aqueous solvent in which the compound (S) is dissolved, and then the solvent is removed. A method of drying, a method of causing a non-aqueous solvent in which the compound (S) is dispersed to undergo electrophoresis in the same manner as the wet electrodeposition method described later, and adhering it to the photoreceptor are also exemplified. Further, the non-aqueous solution of the compound (S) can be uniformly wetted on the surface of the photoreceptor by the ink jet method and then dried to be adsorbed or attached. The ink jet method can be achieved, for example, by the principle and means described in Shin Ohno, “Non-Impact Printing”, CMC (published in 1986). For example, continuous injection type Sweet method, Hertz
Methods, intermittent jet Winston method, ink-on-demand pulse jet method, bubble jet method, ink mist type mist method, etc.

In each case, the compound (S) is used directly or diluted with a solvent instead of the ink and filled in the ink tank and / or the ink head cartridge. Normal ink viscosity is 1-10cP, surface tension is 30-60dyne /
If necessary, a surfactant or the like may be added, and the ink may be heated. In conventional ink jet printers, the orifice system of the head is 3
It is about 0 to 100 μm, and the particle diameter of the flying ink is about the same, but in the present invention, it may be larger than this. In this case, the amount of ink discharged increases, so that the time required for coating can be shortened. Further, the use of multiple nozzles is also extremely effective for shortening the coating time.

On the other hand, silicone rubber can be used as the compound (S). Preferably, it may be wound on a metal core roller to form a silicone rubber roller, which may be directly pressed onto the surface of the photoreceptor. Nip pressure is 0.5-10kgf / cm
^{2. The} contact time may be 1 second to 30 minutes. At this time, the photoconductor and / or the silicone rubber roller may be heated to 150 ° C. or lower. It is considered that a part of the low molecular weight component in the silicone rubber is transferred from the roller surface to the photoreceptor surface by pressing. The silicone rubber may be swollen with silicone oil. The silicone rubber may be sponge-like, or the sponge roller may be further impregnated with silicone oil, a silicone surfactant solution or the like.

In the present invention, these methods are not particularly limited, and various methods are selected depending on the state of the compound (S) used (liquid, waxy substance, solid), and if necessary, a heating medium is used in combination. It is also possible to adjust the fluidity of the compound (S) to be used. The amount of the compound (S) adsorbed on or adhered to the surface of the photoconductor is not particularly limited, and the adverse effect on the electrophotographic characteristics of the photoconductor should not be a practical problem. Usually, a film thickness of 1 μm or less is sufficient, and the adhesive strength of the present invention is expressed by “Weakboundary Layer” (Bikerm
an "The Science of Adhesive Joints" Academic Press
(Defined by 1961) is sufficient.

In the present invention, the compound (S) is adsorbed or adhered on the electrophotographic photosensitive member to impart releasability to the surface, preferably the surface of the surface before the formation of the toner image by the electrophotographic process. It is sufficient that the adhesive strength is 100 g · f or less, and it is not necessary to repeat this step in the color image forming step of the present invention. That is, it may be appropriately carried out according to the combination of the photoreceptor used and the ability to maintain the releasability due to adsorption or adhesion of the compound (S) and the means thereof.

As the constitution and material of the electrophotographic photosensitive member provided in the present invention, any conventionally known constitution can be used,
It is not limited. For example, RMSchaffert, "El
ectrophotography "Focal Press London (1980), SWIn
g, MDTabak, WEHaas, "Electrophotography Fourth
International Conference "SPSE (1983), Isao Shinohara, Hidetoshi Tsuchida, Hideaki Kusagawa," Recording Materials and Photosensitive Resins ", published by Japan Society of Publishing Center (1979), Hiroshi Komon, Chemistry and Industry, 39
(3), 161 (1986), Comprehensive technical data collection "Recent development and practical application of photoconductive materials and photoconductors", Japan Science Information Co., Ltd. (1986), Electrophotographic Society, "Electrophotographic Technology" Basics and Applications ", Corona Publishing Co., Ltd. (1986), The Electrophotographic Society of Japan," Present Symposium on Current Situation of Electrophotographic Photoreceptors for Electrophotography "
The various photoconductors described in the publications and reviews of the above are cited. That is, a single layer consisting of the photoconductive compound itself, or a photoconductive layer in which the photoconductive compound is dispersed in a binder resin,
The dispersed photoconductive layer may be a single layer type or a laminated type.

The photoconductive compound used in the present invention may be either an inorganic compound or an organic compound. Examples of the inorganic compound used as the photoconductive compound of the present invention include zinc oxide, titanium oxide, zinc sulfide,
Examples of conventionally known inorganic photoconductive compounds such as cadmium sulfide, selenium, selenium-tellurium, and silicon lead sulfide, which may form a photoconductive layer together with a binder resin, may also be vapor-deposited or sputtered. Alternatively, the photoconductive layer may be formed alone. When an inorganic photoconductive compound such as zinc oxide or titanium oxide is used as the photoconductive compound, the binder resin is contained in an amount of 10 to 100 parts by weight, preferably 15 parts by weight, based on 100 parts by weight of the inorganic photoconductive compound. ~ 4
Used in a proportion of 0 parts by weight.

On the other hand, the photoconductive layer using an organic compound may be any conventionally known one, specifically, Japanese Patent Publication No.
7-17162, 62-51462, JP-A-52
-24437, 54-19803, 56-107.
Nos. 56-146145 and 6).
0-17751, 60-17752, 60-1
No. 7760, No. 60-254142, No. 62-542
No. 66, a photoconductive layer mainly composed of a charge generating agent, a charge transporting agent and a binding resin, and JP-A-60-
230147, 60-230148, 60-2
Examples thereof include a two-layer photoconductive layer containing a charge generating agent and a charge transporting agent as described in JP-A No. 38853.

The electrophotographic photosensitive member of the present invention may take any form of a photoconductive layer. Examples of the organic photoconductive compound in the present invention include (a) US Pat. No. 3,121,197.
Derivatives described in Japanese Patent No. 3189447, (b) Oxadiazole derivatives described in US Pat. No. 3,189,447, (c) Imidazole derivatives described in Japanese Patent Publication No. 37-16096, and (d) US Patents No. 361540
No. 2, No. 3,820,989, No. 3,542,544, Japanese Patent Publication No. 45-555, No. 51-10983, JP-A No. 51-93224, No. 55-108667.
Nos. 55-156953 and 56-36656, and the like, (e) US Pat. Nos. 3,180,729 and 4,278,746, and JP-A-55-88064 and 55. -88065
No. 49-105537, No. 55-51086,
56-80051, 56-88141, 57.
-45545, 54-112637, 55-7.
Pyrazoline derivatives and pyrazolone derivatives described in Japanese Patent No. 4546, etc., (f) US Pat. No. 3,615,404, Japanese Patent Publication Nos. 51-10105, 46-3712,
No. 47-28336, JP-A-54-83435.
No. 54-110836, No. 54-119925, and the like, phenylenediamine derivatives,

(G) US Pat. Nos. 3,567,450 and 3
No. 180703, No. 340597, No. 365585
No. 0, No. 4232103, No. 4175961, No. 4
No. 012376, Japanese Patent Publication No. Sho 49-35702, West German Patent (DAS) No. 1110518,
JP-B-39-27577, JP-A-55-144250
No. 56-119132, No. 56-22437, etc., arylamine derivatives,
(H) Amino-substituted chalcone derivatives described in US Pat. No. 3,526,501, etc., (i) US Pat. No. 35425
46, etc., N, N-bicarbazyl derivatives, (i) oxazole derivatives described in US Pat. No. 3,257,203, etc., (k) JP-A-56-4623.
4, a styrylanthracene derivative,
(L) Fluorenone derivatives described in JP-A-54-110837, (m) US Pat. No. 3,717,462, JP-A-54-59143 (US Pat. No. 415
(Corresponding to the specification of 0987), JP-A-55-52063.
No. 55, No. 55-52064, No. 55-46760, No. 55-85495, No. 57-11350, No. 57-.
148749, 57-104144, and other hydrazone derivatives described in

(N) US Pat. Nos. 4,047,948 and 4,
047949, 4265990 and 427384.
No. 6, No. 4,299,897, No. 4,306,008, etc. Benzidine derivatives, (o) JP-A-58-
190953, 59-95540, 59-97
148, 59-195658 and 62-3667.
No. 4, stilbene derivatives described in each publication, etc.,
(P) Polyvinylcarbazole and its derivatives described in JP-B-34-10966, (q) JP-B-43-18
Nos. 674 and 43-19192, polyvinylpyrene, polyvinylanthracene, poly-2-vinyl-4- (4'-dimethylaminophenyl) -5-phenyl-oxazole, poly-3-vinyl-N-ethylcarbazole. Vinyl polymers such as (r) JP-B-43-1919
Polymers such as polyacenaphthylene, polyindene, and a copolymer of acenaphthylene and styrene described in JP-A-3, (s)
Condensed resins such as pyrene-formaldehyde resin, bromopyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin described in JP-B-56-13940 and the like, (t) JP-A-56-90833 and 56-
There are various triphenylmethane polymers described in JP-A-161550. In the present invention, the organic photoconductive compound is not limited to the compounds listed in (a) to (t), and all known organic photoconductive compounds can be used. Two or more kinds of these organic photoconductive compounds can be used in combination depending on the case.

As the sensitizing dye contained in the photoconductive layer,
Conventionally known sensitizing dyes used for electrophotographic photoreceptors can be used. These are "Electronic photography" 12 , 9 (1973),
“Organic Synthetic Chemistry” 24 (11), 1010 (1966) and the like. For example, U.S. Pat. Nos. 3,141,770 and 4,283.
475 No. Each specification, JP 48-25658, JP-pyrylium dyes described in JP-A-62-71965 Publication, Applied Optics Supplement 3 50 (1969 ), in JP-50-39548 Patent Publication Described triarylmethane dyes, cyanine dyes described in U.S. Pat. No. 3,597,196 and the like, JP-A-60-163047 and 59.
The styryl dyes described in JP-A-164588, JP-A-60-252517 and the like are advantageously used.

As the charge generating agent contained in the photoconductive layer, various organic and inorganic charge generating agents known in the prior art for electrophotographic photoreceptors can be used. For example, selenium, selenium-tellurium, cadmium sulfide, zinc oxide, and the organic pigments shown in the following (1) to (9) can be used.

(1) US Pat. Nos. 4,436,800 and 4
No. 439506, JP-A-47-37543,
58-123541, 58-192042, 58-219263, 59-78356, 60.
-179746, 61-148453, 61-
No. 238063, Japanese Patent Publication No. 60-5941, No. 6
Azo pigments such as monoazo, bisazo, and trisazo pigments described in JP-A Nos. 0-45664 and (2) U.S. Pat. Nos. 3,397,086 and 4,666,802; Phthalocyanine pigments such as metal-free or metal phthalocyanines described in JP-A Nos. 3 to 7300, (3) US Pat. And the indigo and thioindigo derivatives described in JP-A-47-30331.

(5) Quinaclindone pigments described in British Patent No. 2237679, JP-A No. 47-30332, etc. (6) British Patent No. 2237678, JP-A No. 59-184348, and the same. 62-28738
No. 47-18544, polycyclic quinone pigments described in JP-A Nos. 47-30331 and 47-1.
Bisbenzimidazole pigments described in JP-A-8543, (8) U.S. Pat. Nos. 4,396,610 and 4,644.
No. 082 Squarium salt-based pigments described in each specification,
(9) JP-A-59-53850 and JP-A-61-212254.
And the azurenium salt-based pigments described in Japanese Patent No. 2 and the like. These may be used alone or in combination of two or more.

Further, regarding the mixing ratio of the organic photoconductive compound and the binding resin, the upper limit of the content rate of the organic photoconductive compound is determined by the compatibility between the organic photoconductive compound and the binding resin. Then, crystallization of the organic photoconductive compound occurs, which is not preferable. Since the electrophotographic sensitivity decreases as the content of the organic photoconductive compound decreases, it is preferable to include as many organic photoconductive compounds as possible within the range where crystallization of the organic photoconductive compound does not occur. The content of the organic photoconductive compound is 5 to 120 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the binder resin.

The binder resin (which may be hereinafter referred to as the binder resin (B)) that can be used in the photoreceptor of the present invention may be any of the resins used in conventionally known electrophotographic photoreceptors. The molecular weight is preferably 5 × 10 ³ to 1 × 1
0 ⁶ , more preferably 2 × 10 ^{4 to} 5 × 10 ⁵ . The glass transition point of the binder resin is preferably -40.
C. to 200.degree. C., more preferably -10.degree. C. to 140.degree. For example, Ryuji Shibata and Jiro Ishiwata, Kobunshi, Vol. 17, Vol.
278 (1968) Harumi Miyamoto, Hidehiko Takei, Imaging, 1
973 (No.8), Koichi Nakamura, "Practical Technology of Binders for Recording Materials," Chapter 10, CHC Publishing (1985), The Institute of Electrophotography,
"Present Symposium on Organic Photoreceptors for Electrophotography" Proceedings (1985) edited by Hiroshi Komon, "Recent Development and Practical Use of Photoconductive Materials and Photoreceptors" Japan Science Information Co., Ltd. (1986) The Electrophotographic Society of Japan Volume "Basics and Applications of Electrophotographic Technology" Chapter 5 Corona Publishing Co., Ltd.
(1988), D.Tatt, SCHeidecker, Tappi, 49 (No.1
0), 439 (1966), ESBaltazzi, RGBlanclotte et a
l, Phot. Sci. Eng. 16 (No.5), 354 (1972), Nguyen Chan Kay, Isamu Shimizu, Eiichi Inoue, The Photographic Society of Japan 18 (No.
2), 22 (1980) and the like, compounds and the like described in reviews.

Specifically, olefin polymers and non-polymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and Polymers and copolymers of the derivatives, butadiene-styrene copolymers, isoprene-styrene copolymers, butadiene-unsaturated carboxylic acid ester copolymers, acrylonitrile copolymers, methacrylonitrile copolymers, alkyl vinyl ether copolymers. Polymers, acrylic acid ester polymers and copolymers, methacrylic acid ester polymers and copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, itaconic acid diester polymers and copolymers , Maleic anhydride copolymer, acrylamide copolymer, methacrylamide Polymer, hydroxyl group modified silicone resin, polycarbonate resin, ketone resin, polyester resin, silicone resin, amide resin, hydroxyl group and carboxyl group modified polyester resin, butyral resin, polyvinyl acetal resin, cyclized rubber-methacrylic acid ester copolymer, ring Rubber-acrylic acid ester copolymer, a copolymer containing a nitrogen atom-free heterocycle (as a heterocycle, for example, furan ring, tetrahydrofuran ring, thiophene ring, dioxane ring, dioxofuran ring, lactone ring, benzofuran ring, Benzothiophene ring, 1,3-dioxetane ring, etc.), epoxy resin and the like.

In particular, when a resin having a relatively low molecular weight (about 10 ³ to 10 ⁴ ) containing an acidic group such as a carboxyl group, a sulfo group or a phosphono group is used as a binder resin for the photoconductor, The electrical characteristics can be improved. For example, resins in which the acidic group-containing polymerization component described in JP-A-63-217354 is randomly present in the polymer main chain, JP-A-64-
No. 70761, a resin obtained by bonding an acidic group to one end of the polymer main chain, JP-A-2-67563 and JP-A-2-23.
No. 6561, No. 2-238458, No. 2-23656.
No. 2 and No. 2-247656, etc., and a resin containing an acidic group bonded to the end of the main chain of the graft copolymer, or a resin containing an acidic group in the graft part of the graft copolymer, JP-A No. 1994-242242. The AB type block copolymer containing the acidic group in a block as described in JP-A-3-181948 is mentioned.

Further, in order to make the mechanical strength of the photoconductive layer insufficient by using only these low molecular weight resins,
It is preferable to use another resin having a medium to high molecular weight together. For example, a thermosetting resin forming a crosslinked structure between polymers described in JP-A-2-68561, JP-A-2-68562.
Part of the resin described in JP-A No. 2-6 has a crosslinked structure.
The resin etc. which connect the acidic group of 9759 to the main chain terminal of a graft type copolymer are mentioned. Further, by using a specific medium to high molecular weight resin, stable performance can be maintained even when the environment is significantly changed. For example, JP-A-3-29954, JP-A-3-77954, and JP-A-3-77954. No. 3-206464, which is a resin containing an acidic group described in JP-A No. 92861 and JP-A No. 3-53257, which binds to an end of a graft portion of a graft-type copolymer, or a resin containing an acidic group in a graft portion of the graft-type copolymer. And 3-2237
Examples thereof include a graft type copolymer containing an AB block type copolymer composed of an A block containing an acidic group and a B block containing no acidic group in the graft portion. By using these specific resins, it is possible to uniformly disperse the photoconductor and form a photoconductive layer with good smoothness. In addition, a scanning exposure method using a change in environment or a semiconductor laser beam was used. Even in this case, excellent electrostatic characteristics can be maintained.

The thickness of the photoconductive layer is 1 to 100 μm, especially 1
0 to 50 μm is preferable. When the photoconductive layer is used as the charge generation layer of the laminated type photoreceptor having the charge generation layer and the charge transport layer, the thickness of the charge generation layer is preferably 0.01 to 5 μm, particularly preferably 0.05 to 2 μm. .

In the present invention, various dyes can be used together as a spectral sensitizer depending on the kind of light source such as visible light exposure or semiconductor laser light exposure. For example, Harumi Miyamoto, Hidehiko Takei; Imaging 1973 (No.8) No. 12
Page, CJ Young et al .: RCA Review 15 , 469 pages (1954), Kouhei Kiyota et al .: Transactions of the Institute of Electrical Communication, J63-C (No.2), page 97 (1
980), Yuji Harasaki et al., Journal of Industrial Chemistry, 66 , 78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan, 35 , 208 (1972).
, Etc.) Carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (eg, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanines Examples thereof include dyes (which may contain a metal).

More specifically, as those mainly containing carbonium type dyes, triphenylmethane type dyes, xanthene type dyes and phthalein type dyes, Japanese Patent Publication No. 51-45.
2, JP-A-50-90334 and JP-A-50-11422.
No. 7, No. 53-39130, No. 53-82353, U.S. Pat. Nos. 3,052,540, and 4,054,450.
And those described in JP-A-57-16456. Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes are FM Hamer “The Cyanine Dyes and Relate
d Compounds "and the like can be used, and more specifically, U.S. Pat. Nos. 3,047,384 and 311
No. 0591, No. 3121008, No. 3125447
No. 3128179, No. 3132942, No. 36
No. 22317, British Patent No. 12268892,
Examples thereof include dyes described in JP-A Nos. 1309274 and 1405898, JP-B Nos. 48-7814 and 55-18892.

Further, as a polymethine dye for spectrally sensitizing a near-infrared to infrared light region having a long wavelength of 700 nm or more, JP-A No. 4/1992 has been proposed.
No. 7-840, No. 47-44180, and Japanese Patent Publication No. 51-4
1061, JP-A-49-5034, and JP-A-49-451.
No. 22, No. 57-46245, No. 56-35141.
No. 57-157254, No. 61-26044,
No. 61-27551, U.S. Pat. No. 3,611,915.
4, No. 4,175,956, each specification, "Research Discl
oseure ”, 1982, 216, pages 117-118 and the like. The photoconductor of the present invention is also excellent in that its performance does not easily change depending on the sensitizing dye even when various sensitizing dyes are used in combination.

Further, if necessary, various conventionally known additives for electrophotographic photoreceptors can be used in combination. These additives include chemical sensitizers for improving electrophotographic sensitivity, various plasticizers for improving film properties, surfactants and the like. As a chemical sensitizer,
For example, halogen, benzoquinone, chloranil, fluoranyl, bromanil, dinitrobenzene, anthraquinone, 2,5-dichlorobenzoquinone, nitrophenol, tetrachlorophthalic anhydride, phthalic anhydride, maleic anhydride, N-hydroxymaleimide, N-hydroxyphthalimide. 2,3-dichloro-5,6-dicyanobenzoquinone, dinitrofluorenone, trinitrofluorenone, tetracyanoethylene, nitrobenzoic acid,
Electron-withdrawing compounds such as dinitrobenzoic acid, Hiroshi Komon et al. "Recent Development and Practical Use of Photoconductive Materials and Photoconductors" Chapters 4-6
Chapter: Polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds, and the like, which are cited as references in the Japanese Society for Scientific Information Publishing (1986).
Also, JP-A-58-65439 and JP-A-58-10223.
No. 9, No. 58-129439, No. 62-71965, etc. are also mentioned.

Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, diphenyl phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methyl phthalyl glycolate, dimethyl glycol phthalate. Can be added to improve the flexibility of the photoconductive layer. These plasticizers can be contained in a range that does not deteriorate the electrostatic properties of the photoconductive layer. The addition amount of these various additives is not particularly limited, but is usually 0.1% with respect to 100 parts by weight of the photoconductor.
001 to 2.0 parts by weight.

The photoconductive layer according to the present invention can be provided on a conventionally known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably conductive, and as the conductive support, a substrate such as metal, paper, plastic sheet or the like is impregnated with a low resistance substance as in the conventional case. Conductive treated by, for example, the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided) to have conductivity, and at least one layer coated for the purpose of preventing curling, the support Having a water-resistant adhesive layer on its surface, having at least one precoat layer on the surface layer of the support, if necessary, and laminating a conductive electroconductive plastic substrate on which Al or the like is deposited on paper Etc. can be used. Specifically, as an example of a conductive substrate or a conductive material, Yukio Sakamoto, Electrophotography, 14 (No.1), pp. 2-11 (1975),
Hiroyuki Moriga "Introduction to Special Paper Chemistry" Polymer Publishing (1975), MF Hoover, J. Macromol. Sci. Chem. A-4 (6), 1
The ones described on pages 327 to 1417 (published 1970) are used.

A method for producing a color image of the present invention will be described. As described above, a toner image is formed on the electrophotographic photosensitive member having a peelable surface by a normal electrophotographic process. That is, each process of charging-exposure-developing-fixing is performed by a conventionally known method. Further, when the surface releasability is insufficient, the compound (S) is adsorbed or attached to the surface of the photoreceptor before such a normal electrophotographic process is performed, so that the compound has releasability (releasability). It can be a photoreceptor.

As the developer used in the developing process,
Any conventionally known developer may be used, and examples thereof include a dry developer and a liquid developer. For example, the above-mentioned “Basics and Applications of Electrophotographic Technology”, pages 497 to 505, supervised by Koichi Nakamura, “Development and Practical Use of Toner Material”, Chapter 3 (published by Nihon Kagaku Informatics, 1985
Machida, "Recording Materials and Photosensitive Resins," pages 107-127 (1983), Academic Society Publishing Center, Electrophotographic Society "Imaging No.2-5 Electrophotographic development / fixing / charging."
A specific mode is shown in “Transfer” and the like. As a dry developer, a one-component magnetic toner, a two-component toner, a one-component non-magnetic toner, a capsule toner, or the like is practically used.
Any of these can be used.

Further, as the basic constitution of the material of the concrete wet developer, an electrically insulating organic solvent {for example, isoparaffin aliphatic hydrocarbon: Ansoper H, Isopar G (manufactured by Esso Co.) Shelsol 70, Shelsol 71 (Manufactured by Shell Co.), IP-solvent 1620 (manufactured by Idemitsu Petrochemical Co., Ltd.)} as a dispersion medium, an inorganic or organic pigment or dye as a colorant, an alkyd resin, an acrylic resin, a polyester resin, a styrene butadiene resin, a rosin, etc. And a resin for imparting dispersion stability / fixability and chargeability, and if desired, various additives are added to enhance charge characteristics or improve image characteristics.

Known dyes and pigments can be arbitrarily selected as the colorant, and examples thereof include benzidine type, azo type,
Examples include dyes or pigments such as azomethine-based, xanthene-based, anthraquinone-based, phthalocyanine-based (including metal-containing), titanium white, nigrosine, aniline black and carbon black. Further, as other additives, those specifically described in Yuji Harasaki, "Electrophotography", Vol. 16, No. 2, p. 44 are used. For example, di-2-
Ethylhexyl sulfosuccinic acid metal salt, naphthenic acid metal salt, higher fatty acid metal salt, alkylbenzene sulfonic acid metal salt, alkylphosphoric acid metal salt, lecithin, poly (vinylpyrrolidone), copolymer containing semi-maleic acid amide component, coumarone indene Examples thereof include resins, higher alcohols, polyethers, polysiloxanes and waxes.

The amounts of the main components of these wet type developers are usually as follows. Toner particles composed mainly of a resin (and optionally a coloring agent) are
0.5 to 50 parts by weight is preferable for 1000 parts by weight of the carrier liquid. If it is less than 0.5 parts by weight, the image density will be insufficient, and if it exceeds 50 parts by weight, fog will easily occur in the non-image area. Further, the carrier liquid-soluble resin for stabilizing the dispersion is also used as necessary, and can be added in an amount of about 0.5 to 100 parts by weight with respect to 1000 parts by weight of the carrier liquid. The charge control agent as described above is preferably 0.001 to 1.0 parts by weight with respect to 1000 parts by weight of the carrier liquid. If desired, various additives may be added, and the upper limit of the total amount of these additives is restricted by the electric resistance of the developer. That is, if the electric resistance of the liquid developer with the toner particles removed is lower than 10 ⁸ Ω · cm, it becomes difficult to obtain a high-quality continuous tone image. Therefore, the amount of each additive added is within this limit. It is controlled.

Further, as a specific example of the method for producing a wet developer, a method for producing colored particles by mechanically dispersing a colorant and a resin using a disperser such as a sand mill, a ball mill, a jet mill or an attritor. However, for example, Japanese Patent Publication 35-
5511, Japanese Patent Publication No. 35-13424, Japanese Patent Publication No. 50-
No. 40017, Japanese Patent Publication No. 49-98634, Japanese Patent Publication No. 58
No. 129438 and JP-A No. 61-180248. As another method for producing colored particles, for example, a method of producing dispersed resin particles by a non-aqueous dispersion polymerization method that obtains fine particles having good monodispersity and coloring the resin particles can be mentioned.

As one of the coloring methods, Japanese Patent Application Laid-Open No. 57-4
As described in No. 8738, there is a method of dyeing a dispersed resin with a preferable dye. Further, as another method, as disclosed in JP-A-53-54029,
A method of chemically bonding a dispersion resin and a dye, or, as described in JP-B-44-22955, when using a polymerization granulation method, a monomer containing a dye in advance is used to produce a dye. There is a method of using the contained copolymer.

A combination of the scanning exposure method using laser light which is exposed based on digital information and the developing method using a liquid developer is an effective process because a high-definition image can be formed. An example is shown below. First, the photosensitive material is positioned on the flat bed by the register pin method, and then sucked and fixed by air suction from the back surface. Then, for example, by using the charging device described in "Basics and Applications of Electrophotographic Technology" (edited by the Electrophotographic Society, Corona Publishing Co., Ltd., June 15, 1988), pages 212 and thereafter.
Charge the photosensitive material. The corotron or scotron system is common. At this time, it is also preferable to control the charging condition by giving feedback so that the surface potential is always within a predetermined range based on the information from the charging potential detection means of the photosensitive material. After that, for example,
Scanning exposure with a laser light source is performed using the method described on page 254 and thereafter. First, an image corresponding to a yellow plate out of a color image divided into four colors is converted into a dot pattern and exposed.

Next, a toner image is formed using the liquid developer. The light-sensitive material charged and exposed on a flat bed can be removed from it and the direct wet development method shown on page 275 and after of the cited document can be used. The exposure mode at this time corresponds to the toner image development mode. For example, in the case of reversal development, a negative image, that is, an image portion is irradiated with laser light to charge the photosensitive material with the same charge polarity. The toner having the above is used to apply a developing bias voltage so that the toner is electrodeposited on the exposed portion. The details of the principle are explained on pages 157 and after of the above cited material. After development, in order to remove the excess developer, squeeze as shown on page 283 of the same document is performed, and then dried. It is also preferable to rinse only with the carrier liquid of the developer before squeezing. By repeating the above process for each color of magenta, cyan, and black, a full-color image of four colors can be obtained on the photoconductor.

Next, the toner image on the photosensitive material is thermally transferred onto a primary receptor provided with a peelable transfer layer. First, the transfer layer used in the present invention will be described in detail. The transfer layer of the present invention is not particularly limited as long as it is made of a peelable resin {hereinafter referred to as resin (A)}, is light-transmissive, and can determine the hue of a toner image. It may be colored. When the toner image transferred to the final transfer material is a color image (particularly a full color image), a colorless and transparent transfer layer is usually used.

The resin (A) has a temperature of 180 ° C. or lower or 2
A resin that can be peeled off under a transfer condition of a pressure of 0 kgf / cm ² or less is preferable. If this value is exceeded, it is necessary to increase the size of the transfer device to maintain the heat capacity and pressure of the transfer device in order to separate and transfer the transfer layer from the surface of the primary receptor, or the transfer layer will be separated only under transfer conditions that exceed these conditions. The use of a resin is not preferable because it causes a practically difficult problem such that the transfer speed must be extremely slowed down in order to perform the transfer sufficiently. The lower limit is not particularly limited, but a resin that can be peeled off under a transfer condition of usually room temperature or higher or pressure of 100 gf / cm ² or higher is preferable. The resin (A) may be any as long as it can be peeled off under the above-mentioned transfer conditions.
A resin having a glass transition point of 100 ° C. or less or a softening point of 150 ° C. or less is preferable.

In the present invention, it is preferable to use at least two kinds of resins having different glass transition points or softening points in combination.
In particular, a resin having a glass transition point of 30 ° C. or higher or a softening point of 35 ° C. or higher {hereinafter referred to as a resin (AH)} and a resin having a glass transition point or a softening point of 2 ° C. or higher, particularly 5 ° C. or higher than a resin (AH) {below Resin (AL)} is preferably used in combination. Further, the resin (AL) has a glass transition point of -30 ° C.
It is preferably -40 ° C or a softening point of 0 ° C-45 ° C. Here, the difference in the glass transition point or the softening point in the case where two or more kinds of the resin (AH) or the resin (AL) are contained, the difference between the glass transition point and the softening point in the resin (AH) is the lowest. It is the difference from the one having the highest glass transition point or softening point in (AL). Resin (AH) /
The existence ratio (weight ratio) of the resin (AL) is 5 to 90/95.
It is preferable that it is -10, especially 10-70 / 90-30. If the resin (AH) / resin (AL) abundance ratio deviates from the above range, the effect of the combined use decreases.

Further, the transfer layer of the present invention comprises the first resin (AH) having a high glass transition point on the surface of the primary receptor.
It is preferably formed by a layer, and a second layer of a resin (AL) having a low glass transition point on the layer. As a result, the transferability from the primary receptor to the final transfer material is further improved, the latitude of the transfer conditions (heating temperature, pressure, transport speed, etc.) is expanded, and the final transfer material becomes a color image copy. It is possible to easily perform the transfer regardless of the type. Further, since the surface side of the transfer layer transferred to the final transfer material is composed of a resin (AH) having a high glass transition point, filing suitability (adhesion etc. which occurs when a file is sandwiched between plastic sheets, etc.) Problem) becomes even better. Further, by selecting the type of the resin (AH), it becomes possible to impart the writing property and the imprinting property similar to those of plain paper.

Specific examples of the resin (A) that can be used in the transfer layer include thermoplastic resins, resins known as adhesives or pressure-sensitive adhesives, such as olefin polymers and copolymers, and vinyl chloride. Copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, polymers and copolymers of styrene and its derivatives, olefin-styrene copolymers, olefins -Unsaturated carboxylic acid ester copolymer, acrylonitrile copolymer, methacrylonitrile copolymer, alkyl vinyl ether copolymer, acrylic acid ester polymer and copolymer, methacrylic acid ester polymer and copolymer, styrene- Acrylic ester copolymer, styrene-methacrylic acid ester copolymer, itaconic acid diester copolymer Body and copolymers, maleic anhydride copolymers, acrylamide copolymers, methacrylamide copolymers, hydroxy group-modified silicone resins, polycarbonate resins, ketone resins, polyester resins, silicone resins,
Amide resin, hydroxyl group- and carboxyl group-modified polyester resin, butyral resin, polyvinyl acetal resin,
Cyclized rubber-methacrylic acid ester copolymer, cyclized rubber-
Acrylic ester copolymer, copolymer containing a heterocycle (for example, a furan ring, a tetrahydrofuran ring, a thiophene ring, a dioxane ring, a dioxofuran ring, a lactone ring, a benzofuran ring, a benzothiophene ring, 1,3- Dioxetane ring, etc.), cellulose resin,
Examples thereof include fatty acid-modified cellulose-based resins and epoxy resins.

[0131] For example, Volumes 1 to 18 (1981) of "Plastic Materials Course Series" published by Nikkan Kogyo Shimbun, "Polyvinyl Chloride" edited by Kinki Chemical Society Vinyl Section, published by Nikkan Kogyo Shimbun (1988), Hide Omori Three "Functional Acrylic Resins" Techno System Co., Ltd. (1985), Eiichiro Takiyama "Polyester Resin Handbook" Nikkan Kogyosha (1988), Kazuo Yuki "Saturated Polyester Resin Handbook" Nikkan Kogyo Shimbun (1989) ), "Polymer Data Handbook <Applications>" edited by The Polymer Society of Japan, Chapter 1 Baifukan (1986), Yuji Harazaki "Latest Binder Technology Handbook" Chapter 2 General Technology Center Co., Ltd. (1985), Tadashi Okuda "Polymer processing separate volume 8 20th"
Volume Special Issue "Adhesive" Polymer Publishing (1976), Keiji Fukuzawa "Adhesive Technology" Polymer Publishing (1987), Mamoru Nishiguchi "Adhesion Handbook 14th Edition" Polymer Publishing (1985), Japan "Adhesion Hattond Book 2nd Edition" edited by Adhesion Association, Nikkan Kogyo Shimbun (1980
Years) and the like.

The resin (A) is obtained by adding the polymer component (f) containing a substituent containing a fluorine atom and / or a silicon atom, which has the effect of improving the releasability of the resin (A) itself, to the above-mentioned resin. You may further contain as a polymer component. This improves the releasability of the releasable surface from the primary receptor, resulting in better transferability. The content thereof is preferably 3 to 40% by weight, more preferably 5 to 25% by weight, based on 100 parts by weight of the total polymer component of the resin (A). The substituent may be incorporated in the polymer main chain of the polymer, or may be present as a substituent of the side chain of the polymer. Preferably, the polymer component (f) is
It is contained as a block in the copolymer of the resin (A).

As described above, the resin (A) constituting the transfer layer
Is composed of two or more kinds of resins having different glass transition points or softening points, the resin containing the fluorine atom and / or silicon atom-containing polymer component (f) is a resin having a high glass transition point (AH) and Low glass transition point resin (AL)
Which has a high glass transition point on the surface of the primary receptor (AH) and a second layer of resin (AL) having a low glass transition point thereon.
When it is formed of multiple layers, it is more effective if it is contained in the resin (AH). The transferability improving effect and the image strength improving effect are further exhibited. Specific examples of the polymer component (f) include those similar to the polymer component that can be contained in the resin (P) used in the photosensitive layer having the above-mentioned releasability.

As a preferred embodiment of the so-called block copolymer in the resin (A), in the block copolymer, the fluorine atom and / or silicon atom-containing polymer component (f) is composed of blocks. It doesn't matter. Here, being composed of blocks means that the polymer has a polymer segment containing 70% by weight or more of a fluorine atom and / or a silicon atom. For example, as described in the resin (P), , AB type blocks, ABA type blocks, BAB type blocks, graft type blocks or star type blocks. These various block copolymers (A) can be synthesized according to a conventionally known polymerization method, and specifically, the same methods as those cited for the resin (P) containing the polymer component in a block can be used. Can be mentioned. The resin (A) is preferably used in an amount of 70% by weight or more, and more preferably 90% by weight or more in the total amount of the composition of the transfer layer.

If desired, other additives may be added to the transfer layer in order to improve various physical properties such as adhesion, film-forming property and film strength. For example, polybutene, DOP, DBP, low-molecular-weight styrene resin, low-molecular-weight polyethylene as a plasticizer and a softening agent for improving wettability to a photoreceptor and lowering melt viscosity, such as rosin, petroleum resin, and silicone oil for adjusting adhesion. High molecular weight hindered polyphenols, triazine derivatives and the like can be added as antioxidants such as wax, microcrystalline wax and paraffin wax. For more information, see “Practice of Hot Melt Adhesion” (Hiroshi Fukada, Kobunshi Kogakukai, published in 1983) 29-
See page 107. The total thickness of the transfer layer is 0.1
-20 μm is suitable, preferably 0.5-10 μm
Is.

On the other hand, the primary receptor transfers the toner image formed on the surface of the photoconductor onto the transfer layer in close contact with the electrostatic transfer method or under heating and / or pressure, and further transfers it onto the final transfer material. It serves as an intermediate medium for peeling and transferring the transfer layer on which the toner image is formed under heating and / or pressure to form a final color image. Therefore, it is important that the releasability of the surface of the primary selector is lower than that of the surface of the photoconductor and that the releasability of peeling and transferring to the final transfer material is maintained, and that it is larger than the adhesive force of the surface of the photoconductor,
It is desirable that it is 0 g · f or more, and more preferably 50 g · f or more. The maximum adhesive force on the receptor surface is preferably 250 g · f, more preferably 2
It is less than 00g · f.

In order to adjust the adhesive force, a primary receptor satisfying the above adhesive force may be used in advance, or the above-mentioned releasing compound (S) may be applied to the surface of the primary receptor before forming the transfer layer. It may be applied or adhered to adjust the adhesion of the surface of the primary receptor. The compound (S) to be used and its application method are the same as in the case of applying the compound (S) to the above-mentioned photoconductor to impart releasability to the photoconductor. The device for applying the compound (S) to the photoreceptor may be used in combination on the primary receptor, or a separate device may be set.

Further, when the transfer layer is formed on the primary receptor by the electrodeposition coating method, an electrically insulating organic solvent having a relative dielectric constant of 3.5 or less is added to at least 1.0 liter of the organic solvent. 0.01 g of at least one compound (S) containing a fluorine atom and / or a silicon atom that dissolves, and having a glass transition point of 140 ° C. or lower or a softening point of 180 ° C.
A transfer layer that can be peeled off on a primary receptor by electrocoating or adhering resin particles (AR) by electrophoresis using a resin particle dispersion liquid for electrodeposition in which the following resin particles (AR) are dispersed to form a film. Can be formed. The releasable compound (S) contained in the electrodeposition dispersion liquid for forming the transfer layer is adsorbed to the primary receptor before the dispersed resin particles (AR) are electrophoresed and electrodeposited on the surface of the primary receptor. Alternatively, since it adheres, it can be a primary receptor having an adjusted adhesive force before the transfer layer is formed. Specific details will be described later.

Any material may be used as long as it is a primary receptor satisfying the above conditions. In the present invention, examples of the method used for transferring the toner image from the photoreceptor to the primary receptor include a drum method and an endless belt method that can be repeatedly used. In the drum system or the endless belt system, the material of the primary receptor to be provided on the drum may be any material satisfying the above conditions, but in a preferred embodiment, the elastic layer and / or the elastic layer and the reinforcing layer. A laminated structure including a support is desirable, and the surface of the laminated structure may satisfy the above physical properties. These stacks may be provided directly on the drum, for example, or they may be removable so that they can be replaced.

Examples of the elastic body include conventionally known natural resins and synthetic resins, which may be used alone or in combination of two or more kinds to form a single layer or a plurality of layers. For example, AD Roberts "Natural Rubber Science an
d Technology ”Oxford Science Publications (1988), W. Hofmann,“ Rubber Technology Handbook ”, Ha
nser Publishers (published in 1989), plastic material structure,
Various resins are described in all 18 volumes, Nikkan Kogyo Shimbun, etc. For example, styrene-butadiene rubber, butadiene rubber, acrylonitrile-butadiene rubber, cyclized rubber, chloroprene rubber, ethylene-propylene rubber, butyl rubber, chlorosulfonated polyethylene rubber, silicone rubber, fluororubber, polysulfide rubber, natural rubber, isoprene rubber, Examples of the urethane rubber include, but are not limited to, urethane rubber and the like, and can be arbitrarily selected in consideration of releasability from the transfer layer, durability, and the like. Further, the adhesion of the receptor surface can be easily adjusted by the same method as described for the easily peelable photoreceptor.

As the reinforcing layer for the elastic layer, cloth, glass fiber, resin-impregnated special paper, aluminum, stainless steel or the like is used. A sponge-like rubber layer may be provided between the surface elastic layer and the reinforcing layer. The average roughness of the surface of the primary receptor is preferably 0.01 mm or less, and the thickness of the surface elastic layer is preferably 0.01 mm to 10 mm. In the endless belt system, a known belt type primary receptor member can be used. For example, US Pat. Nos. 3,893,761, 4,684,238 and 4,690,539 can be used. And the like. Further, a method of providing a layer serving as a heating medium in the layer of the belt carrier of the belt type primary receptor is also mentioned, and for example, the method described in JP-A-4-503265 is known.

In the present invention, the transfer layer must be provided on the primary receptor by the end of the toner image forming process on the photoreceptor. In the present invention, a primary receptor having a peelable transfer layer provided on the surface thereof in advance may be used, but the transfer layer is preferably formed in the electrophotographic apparatus, such as a hot melt coating method and an electrodeposition coating method. And at least one of the transfer methods. This allows
This transfer layer forming apparatus can be incorporated in an apparatus for performing an electrophotographic process, and the primary receptor can be repeatedly used in the same apparatus, and the steps can be continuously performed without disposing of the primary receptor. it can.
As a result, there is an advantage that the cost of the color copy to be produced can be significantly reduced.

Each transfer layer forming method will be described in detail below. The hot-melt coating (hot-melt) method is a method in which a transfer layer composition is hot-melt coated by a known method, and it is a solventless coating machine, for example, the above-mentioned document “Actual Hot Melt Adhesion”.
The mechanism of the hot melt coating apparatus for hot melt adhesives (hot melt coater) described on pages 197 to 215 can be converted to the drum coating specification of the primary receptor. For example,
A direct roll coater, an offset gravure roll coater, a lot coater, an extrusion coater, a slot orifice coater, a curtain coater and the like can be mentioned. The melting temperature of the thermoplastic resin at the time of application is optimized depending on the component composition of the thermoplastic resin used, but it is usually in the range of 50 to 180 ° C. After pre-melting with a preheating device having a closed automatic temperature control means,
It is desirable to raise the temperature to a suitable temperature in a short time at the position where it is applied to the primary receptor. By doing so, it is possible to prevent deterioration and coating unevenness of the thermoplastic resin due to thermal oxidation. The coating speed depends on the fluidity of the thermoplastic resin at the time of heat melting, the coater method, the coating amount, etc., but is preferably 1 to 10 mm / sec, more preferably 5 to 40 mm / sec.

The transfer method is a method of transferring a transfer layer held on a releasable support typified by release paper (hereinafter referred to as release paper) onto a primary receptor. After forming a transfer layer on release paper by hot melt coating, solvent coating, latex electrodeposition, etc., the transfer layer is thermally transferred onto the surface of the primary receptor. The release paper (release paper) on which the transfer layer is formed is roll-shaped or sheet-shaped and can be easily supplied into the transfer device. As the release paper used in this method, any conventionally known release paper can be used. For example, new technology of adhesion (adhesive adhesion) and its use / development materials for various applied products (issued by: Management Development Center Publishing Department, May 20, 1978), published by All Paper Guide Paper Product Encyclopedia, Volume 1, Culture Industry Edition; Paper Industry Times Co., Ltd., December 1, 1983) Can be mentioned. Specifically, as release paper, a release agent mainly composed of silicone was applied to unbleached Clupak paper laminated with polyethylene resin, high-grade paper precoated with solvent-resistant resin, kraft paper, and undercoat. It is applied on PET base or glassine paper directly. In general, a solvent type silicone is used, and the silicone is applied at a concentration of 3 to 7% by a gravure roll or wire bar method, dried, and then heat-treated at 150 ° C. or higher to be cured. The coating amount is about 1 g / m ² .

As the release paper, tapes, labels, forming industry and cast coat industry, which are generally commercially available from paper makers, can be used. For example, separate paper (Oji Paper), Kingleys (Shikoku Paper),
Examples include Sun Release (Sanyo Kokusaku Pulp) and NK High Release (Nippon Kogyo Paper Co., Ltd.). In order to form a transfer layer on release paper, a transfer layer composition containing a thermoplastic resin (A) as a main component is applied by bar coating, spin coating,
It is easily performed by applying a film by spray coating or the like. For thermal transfer of the transfer layer on the release paper onto the primary receptor, conventional thermal transfer methods can be used. That is, the release paper holding the transfer layer may be pressure-bonded to the primary receptor to thermally transfer the transfer layer. For this purpose, for example, FIG.
A device as shown in FIG.

Next, the electrodeposition coating method will be described. In this method, the above-mentioned thermoplastic resin (A) is electrodeposited in the form of resin particles on the surface of the primary receptor, and a uniform thin film is formed, for example, by heating to form a transfer layer. Therefore, it is necessary that the thermoplastic resin particles have either a positive charge or a negative charge, and the electroscopic property is arbitrarily determined by the charge properties of the primary receptors to be combined. The resin particles are in a range satisfying the above-mentioned physical properties, and usually have an average particle diameter of 0.01 μm to 1
5 μm, preferably 0.05 μm to 5 μm
m, more preferably 0.1 μm to 1 μm. . The particles may be in the form of particle powder (dry type) or non-aqueous resin particles (wet type). Preferred are non-aqueous dispersed resin particles, which can easily adjust the film thickness of the peeling transfer layer to a thin film with a uniform thickness.

Particularly, at least two kinds of resins having different glass transition points, preferably the above-mentioned resins having a high glass transition point (A
A transfer layer formed by using resin particles {hereinafter particularly referred to as resin particles (ARW)} containing H) and at least two kinds of resins having a low glass transition point (AL) in the same particle. Transferability is further improved.

The resin particles used in the present invention can be produced by a conventionally known mechanical grinding method or polymerization granulation method. In these production methods, particles of either dry electrodeposition or wet electrodeposition can be used. In producing fine particles used in the dry electrodeposition method,
Examples of the mechanical pulverization method include a method of directly pulverizing with a conventionally known pulverizer to obtain fine particles (for example, a method using a ball mill, a paint shaker, a jet mill, etc.), and if necessary, forming resin particles. The materials can be mixed, pulverized through melting and kneading, or classified for grading the particle diameter after pulverization, or post-treatment for treating the surface of the particles can be appropriately combined. A spray dry method is also known. Specifically, "Granulation Handbook", Part II, edited by Japan Powder Industry Technology Association (Ohmsha, 1991)
Year), Kanagawa Management Development Center "Practice of the latest granulation technology"
(Kanagawa Business Development Center Publishing Department, 1984), Masafumi Arakawa et al. "Latest powder design technology" Techno System Co., Ltd.
(1988) and the like, and can be easily produced by appropriately using the methods described in detail in the textbooks.

As the polymerization granulation method, conventionally known methods such as an emulsion polymerization reaction carried out in an aqueous system, a seed polymerization reaction, a suspension polymerization reaction and a dispersion polymerization reaction carried out in a non-aqueous solvent system are known. Specifically, Soichi Muroi "Chemistry of Polymer Latex" Polymer Publishing (1970), Taira Okuda, Hiroshi Inagaki "Synthetic Resin Emulsion" Polymer Publishing (1978), Soichi Muroi "Polymer Latex""Introduction" Kobunsha (1983), I.
Piirma, PC Wang "Emulsion Polymerization" I. Piirm
a & JLGardon, ACS symp. Sev. 24, p.34 (1974
Fumio Kitahara et al. "Chemistry of Dispersed Emulsion Systems" Engineering Book (1979)
), Soichi Muroi's supervision, "Cutting-edge technology of ultrafine polymer"
CMC (1991), etc., after being made into particles by the method described in the textbooks, and then collected and powdered by various methods as described in the above-mentioned mechanical method textbooks to manufacture. it can.

As a method of dry electrodeposition of the obtained fine particle powder, a conventionally known coating method of electrostatic powder or a developing method of a dry electrostatic photograph developer can be used. Specifically, as described in "Electrostatic Powder Coating" by JF Hughes (Translated by Hideo Nagasaka and Machiko Midorikawa), charging by methods such as corona charging, friction charging, induction charging, ionic wind charging, and reverse ionization phenomenon is used. As described in the textbooks such as "Method of Electrodeposition of Fine Particles", "Development and Practical Use of Recent Electrophotographic Development System and Toner Material", Chapter 1 (Japan Science Information Co., Ltd., 1985) edited by Koichi Nakamura. Cascade method, magnetic brush method, fur brush method, electrostatic method, induction method,
This can be appropriately performed using a development method such as a touchdown method or a powder cloud method.

When the non-aqueous latex used in the wet electrodeposition method is produced, either the mechanical method or the polymerization granulation method can be used as described above. For example, a method in which a dispersion polymer is used in combination and further dispersed by a wet disperser (for example, a ball mill / paint shaker, Keddy mill, Dynomill, etc.), a material to be a resin particle component and a dispersion assisting polymer (or coating polymer) are kneaded in advance. And the like, and then pulverized, and then a dispersing polymer is coexisted and dispersed. Specifically, a method for producing a paint or a developer for electrostatic photography can be used. For example, "Flow of Paint and Dispersion of Paint" translated by Kenji Ueki, Kyoritsu Publishing (1971
), "Solomon, Science of Paint", "Paint and Surfac
e Coating Theory and Practice ", Yuji Harazaki" Coating Engineering "Asakura Shoten (1971), Yuji Harasaki" Basic Science of Coating "(1977) and other publications.

As the polymerization granulation method, a conventionally known non-aqueous dispersion polymerization method can be used. Specifically,
"Latest Technology of Ultrafine Polymer", Chapter 2, "Recent Electrophotographic Development System and Development and Practical Use of Toner Materials"
Chapter 3, KEJ Barvett "Dispersion Polymerization i
n Organic Media "John Wiley (1975) and other books.

As described above, resin particles (A) containing at least two kinds of resins having different glass transition points in the same particle.
When RW) is obtained, it can be easily produced by using a seed polymerization method. Specifically, the fine particles of the resin (AL) or (AH) are first synthesized by the above-described conventionally known non-aqueous dispersion polymerization method, and then the fine particles are used as seeds, and the seed and glass transition are performed in the same manner as above. A method of producing by feeding and polymerizing monomers corresponding to resins having different points (for example, resin (AH) or (AL) respectively) is preferable.

In the polymerization granulation method, in order to introduce the polymer component (f) into the resin (A) for improving the releasability, the polymer component is soluble in the organic solvent which becomes the thermoplastic resin and is polymerized. A monomer corresponding to the polymer component (f) is allowed to coexist with the insolubilizing monomer to carry out a polymerization reaction, whereby the resin is copolymerized in the resin (A) to easily obtain resin particles of a random copolymer. To be

Further, in order to introduce the polymer component (f) in the block of the polymer, a method of using at least a block copolymer containing the polymer component (f) in the block in the dispersion stabilizing resin to be used, Or a weight average molecular weight of 1 × 10 ³ having the polymer component (f) as a main repeating unit.
˜2 × 10 ⁴ (preferably 3 × 10 ^{3 to} 1.5 × 10 ⁴ ) monofunctional macromonomers are coexistent and copolymerized with the monomers to facilitate the resin (A) block copolymerization. Can be coalesced. Further, as another method, a polymer initiator containing the polymer component (f) as a main repeating unit (azobis polymer initiator or peroxide polymer initiator)
Also by using, the resin particles of the block copolymer can be similarly obtained.

The non-aqueous solvent used in the production of the non-aqueous solvent-based dispersed resin particles may be any organic solvent having a boiling point of 200 ° C. or lower, and may be used alone or in admixture of two or more. Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ketones such as diethyl ketone, diethyl ether,
Tetrahydrofuran, dioxane, and other ethers, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and other carboxylic acid esters, hexane, octane, decane, dodecane, tridecane, cyclohexane, cyclooctane, and other fatty acids having 6 to 14 carbon atoms Examples thereof include aromatic hydrocarbons such as group hydrocarbons, benzene, toluene, xylene, chlorobenzene, and halogenated hydrocarbons such as methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, dichloropropane, and trichloroethane. However, it is not limited to the above-mentioned compound examples.

By synthesizing dispersed resin particles in these non-aqueous solvent systems by the dispersion polymerization method, the average particle size of the resin particles easily becomes 1 μm or less, and the particle size distribution is very narrow and monodisperse particles. Can be Since these non-aqueous dispersion resin particles are subjected to a wet electrostatic development method or a method in which they are electrophoresed in a pressure field of an electric field, they are used as a dispersion medium at the time of electrodeposition.
It is adjusted to a non-aqueous solvent system of ⁸ Ω · cm or more and a dielectric constant of 3.5 or less. Specifically, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons, and halogen-substituted products thereof can be used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, Isopar E, Isopar G, Isopar H, Isopar L (Isoper; product of Exxon Corporation Name), Shersol 70, Shersol 71
(Shellsol; trade name of Shell Oil Co.), Amsco OMS, Amsco 460 solvent (Amsco; American
Mineral Spirits Inc.) and the like can be used alone or in combination.

Therefore, as the solvent used in the polymerization granulation,
It is preferable to use the insulating organic solvent from the beginning, but it is also possible to adjust by adjusting the dispersion medium after granulating with a solvent other than these solvents. As another method of synthesizing the non-aqueous latex, the above-mentioned electric resistance of 10 ⁸ Ω · c is used.
By wet-dispersing a block copolymer composed of a polymer component that is soluble in a non-aqueous solvent having a dielectric constant of 3.5 or more and 3.5 or less and a polymer component that is insoluble in the solvent in the solvent It can also be provided as fine resin particles. That is, a block copolymer consisting of a soluble polymer component and an insoluble polymer component was made into a polymer in the organic solvent in which the block copolymer was previously dissolved, by using the block polymer synthesis method described above. After that, it is a method of dispersing in a non-aqueous solvent for electrodeposition.

As described above, in order to electrophoretically disperse the dispersed particles in the dispersion medium, the particles are positively-charged or negatively-charged electro-detecting particles, and a technique for imparting electro-detecting properties to the particles. Is
This can be achieved by appropriately using the technique of the developer for wet electrostatic photography. Specifically, "Recent Development and Practical Use of Electrophotographic Development Systems and Toner Materials" 139-148, "Basics and Applications of Electrophotographic Technology" edited by The Institute of Electrophotography, 497-505 (Corona Publishing Co., 1988 Annual), Yuji Harasaki "Electronic Photography" 16 (No.
2), page 44 (1977), etc., and using other electro-detection materials and other additives. For example, British Patent No. 89
3,429, 934,038, U.S. Pat. No. 1,1.
22,397, 3,900,412, 4,60
6,989, JP-A-60-179751, JP-A-60-
No. 185963, JP-A No. 2-13965, and the like.

The composition of the non-aqueous latex used for electrodeposition is usually such that at least 1 liter of the electrically insulating dispersion medium contains 0.1 to 10 particles mainly containing a thermoplastic resin.
20 g, 0.01 to 50 g of the dispersion stabilizing resin, and 0.0001 to 10 g of the charge control agent added as necessary. Further, other additives may be added in order to maintain the dispersion stability and charge stability of the particles, for example, rosin, petroleum resin, higher alcohols, polyethers, silicone oils, paraffin wax. And triazine derivatives. However, it is not limited to these.

The upper limit of the total amount of these additives is regulated by the electric resistance of the latex for electrodeposition. That is, when the electric resistance is lower than 10 ⁸ Ω · cm, it becomes difficult to obtain a sufficient amount of the thermoplastic resin particles to be adhered, so the amount of each additive added is controlled within this limit. Thus, the thermoplastic resin particles which are made into fine particles and imparted with a charge and dispersed in the electrically insulating liquid exhibit the same behavior as that of the electrophotographic wet developer. Therefore, for example, it is possible to perform electrophoresis on the surface of the primary receptor using a developing device, for example, a slit developing electrode device described in "Basics and Applications of Electrophotographic Technology", pages 275 to 285, cited above. That is, particles mainly containing a thermoplastic resin are supplied between a counter electrode and a counter electrode placed opposite to the primary receptor, and are electrophoresed according to a potential gradient applied from an external power source to be attached or electrodeposited on the primary receptor. To be formed.

Generally, when the particles are positively charged, a voltage is applied from an external power source between the conductive support of the primary receptor and the developing electrode of the developing device so that the primary receptor side has a negative potential. And electrostatically electrodeposit the particles onto the primary receptor surface. It is also possible to perform electrodeposition by wet toner development by a usual electrophotographic process.
That is, as shown in the premise "Basics and Applications of Electrophotographic Technology", pages 46 to 79, the primary receptor is uniformly charged and then the normal wet toner development is performed. The amount of the thermoplastic resin particles deposited on the primary receptor can be arbitrarily adjusted by the applied voltage of the external bias, the charging potential of the primary receptor, the developing time and the like. After electrodeposition, the developer is wiped off by a squeeze using a known rubber roller, gap roller, reverse roller or the like.
Methods such as corona quiz and air squeeze are also known. Further, it is dried with cold air or hot air, or with an infrared lamp or the like, and preferably thermoplastic resin particles are formed into a film to form a transfer layer. The thickness of the transfer layer at this time is preferably in the range of 0.1 to 10 g / m ² , and more preferably 0.5.
~ 5 g / m ² .

Furthermore, in the present invention, when the transfer layer is formed on the primary receptor, the compound (S) containing at least a fluorine atom and / or a silicon atom is contained in the electrodeposition dispersion liquid for forming the transfer layer. This makes it possible to adjust the adhesive force of the primary receptor and form the transfer layer at the same time. The compound (S) used here is the same compound as described for the releasable compound (S) described above, and at least with respect to 1 liter of the electrically insulating organic solvent having a relative dielectric constant of 3.5 or less. Melts more than 0.01g (Temperature 25 ℃)
It is a thing. When the amount of the compound (S) dissolved in 1 liter of the solvent is less than 0.01 g, the adsorption of the primary receptor of the compound (S) tends to be uneven, which is not preferable.
The compound (S) is a solution prepared by dissolving the compound (S) at a concentration of 0.01 g / l in the electrically insulating organic solvent described above, after wetting the primary receptor to be used, and after touch-drying, JIS Z
Any compound may be used as long as the adhesive force according to the “Adhesive tape / adhesive sheet test method” of 0237-1980 can be adjusted to the above value. The addition amount of the compound (S) in the electrically insulating organic solvent varies depending on the compound (S) and the electrically insulating organic solvent used, etc., but satisfies the above physical properties and adversely affects the electrophoresis of the resin particles (liquid resistance). Decrease, increase in clay, etc.)
It is added in the range that does not reach. Preferably 0.01-
It is about 20 g / liter.

In the present invention, the three methods described above can be mentioned as preferable methods for forming the transfer layer. However, the wet electrodeposition method is used because the transfer apparatus can be simplified and a uniform thin film can be formed stably and easily. Particularly preferred.

A known method and apparatus can be used for the thermal transfer of the transfer layer. The nip pressure during transfer is 0.
^{2 to 20} kgf / cm ² , more preferably 0.5 to 15 kgf / cm ²
As the roller pressing means, springs or air cylinders using compressed air at both ends of the roller shaft can be used. Transport speed is 0.1-100mm
/ Sec, more preferably 0.5 to 50 mm / sec, and may be different in the electrophotographic process and the thermal transfer process.

Next, in the present invention, the toner image on the primary receptor is thermally transferred together with the transfer layer to the final transfer material. The final transfer material used in the present invention is not particularly limited, and includes high-quality paper, coated paper, natural paper such as art paper,
Synthetic paper support, reflective pigment such as metal support such as aluminum, iron and SUS, transmissive material such as resin film (plastic film) such as polyester, polyolefin, polyvinyl chloride and polyacetate Good.

A publicly known method and apparatus can be used for this thermal transfer. The preferable heating temperature range at the time of transfer, the range of the nip pressure between the primary receptor and the material to be transferred, and the range of the transport speed are the same as the ranges of the thermal transfer conditions of the photoreceptor and the primary receptor described above. Further, the transfer to the primary receptor and the transfer to the transfer material may be the same or different. The transfer of the toner image from the photoconductor to the primary receptor and the transfer of each transfer layer from the primary receptor to the final transfer material may be simultaneous within one screen, or the transfer of the entire one screen to the primary receptor is completed. Then, it may be transferred to the final transfer target material. The thermal transfer behavior to the final transfer material is estimated as follows. That is, when the transfer layer softened to some extent is heated, the tackiness increases, and the transfer layer adheres to the final transfer material. Next, after passing under the peeling roller, the temperature is lowered, the fluidity and the tackiness are reduced, and the toner image is peeled off from the surface of the primary receptor while being adhered to the final transfer material together with the toner image. Therefore, the conditions should be set so that such a state is realized. Since the toner image on the final transfer material is eventually overcoated with the transfer layer, the toner image can be protected from scratches and stains.

The electrophotographic color image forming method of the present invention will be described in detail below with reference to the accompanying drawings. FIG. 2 is a schematic view of an electrophotographic color image forming apparatus for carrying out the method of the present invention, which uses a drum system as the primary receptor 20. As described above, when the electrophotographic photosensitive member whose surface is modified to be peelable is used, a toner image is formed on the photosensitive member 11 by a normal electrophotographic process. When the surface releasability is insufficient, the surface of the photoreceptor 11 can be provided with releasability by providing a device for adsorbing or adhering the compound (S) before the electrophotographic process. it can. That is, the compound (S) coating unit 10 using any one of the above-described specific modes is used to form the photoreceptor 11
The compound (S) is supplied to the surface. The coating unit 10 for adsorbing or adhering the compound (S) onto the surface of the photoreceptor may be fixed or movable.

As described above, the development in the present invention may be carried out with either a dry developer or a wet developer, but a copy image obtained by the method using a wet developer gives a higher resolution image. Therefore, a specific embodiment will be described below by taking the case of using a wet developing unit as the developing unit as an example. The wet developing unit set 14 is movable. The unit set 14 further includes liquid developing units 14Y, 14M, 14C and 14K containing wet developers of yellow, magenta, cyan and black, respectively. Each may be provided with a pre-bath, a rinse, and a squeeze means for the purpose of preventing the non-image area from being soiled. A carrier liquid of a wet developer is usually used as the pre-bath and rinse liquid.

First, the photoreceptor 11 is the corona charging device 18
Then, for example, after being uniformly charged positively, when the image is first exposed by the exposure device (for example, a semiconductor laser) 19 based on the image information of yellow, the potential of the exposed portion is reduced and the potential between the unexposed portion is reduced. Potential contrast is obtained. Only the yellow liquid developing unit 14Y containing a liquid developer in which a yellow pigment having a positive electrostatic charge is dispersed in an electrically insulating dispersion medium is brought close to the surface of the photoconductor 11 from the wet developing unit set 14 and the gap is set to 1 mm. To fix.

First, the photoconductor 11 is pre-bused by the pre-bus means provided in the developing unit, and then wet type while applying a developing bias voltage between the photo conductor and the developing electrode by a bias power source and electric connection not shown. A developer is supplied to the surface of the photoconductor. At this time, the bias voltage is connected so that the developing electrode side is positive and the photoconductor side is negative, and the applied voltage is slightly lower than the surface potential of the unexposed portion. If the applied voltage is too low, a sufficient toner image density cannot be obtained.
After that, the rinsing means built in the developing unit 14 is used to wash off the developing solution adhering to the surface of the photoconductor, and then the squeeze means is used to remove the rinsing solution adhering to the surface of the photoconductor, and then it is passed under the intake / exhaust unit 15. To dry. The above steps are repeated for magenta (14M), cyan (14C), and black (14K) to obtain a color toner image on the photoconductor 11. During this time, the primary receptor 20 is placed away from the surface of the photoconductor 11.

On the other hand, the transfer layer 22 is provided on the primary receptor 20 by the transfer layer forming device 21 by the end of the process of forming a toner image on the photoreceptor. If necessary, the compound (S) is adsorbed or attached to the surface of the primary receptor 20 before forming the transfer layer. The coating unit 10 may be movable and used together.

Taking the case of the wet electrodeposition method as an example, the transfer layer 22
The formation of The electrodeposition unit containing the dispersion liquid of resin particles is brought close to the primary receptor 20 and fixed so that the distance between the electrodeposition unit and the developing electrode is 1 mm. The particle dispersion liquid is supplied into this gap and rotated while applying a voltage from the outside so that the particles are adsorbed on the entire surface of the primary receptor 20. The squeeze device incorporated in the electrodeposition unit removes the particle dispersion adhering to the surface of the primary receptor 20, and then the resin particles are heat-melted by a heating means to obtain a film-formed resin transfer layer. At this time, in order to exhaust the dispersion solvent of the dispersion liquid, the intake / exhaust unit 15 provided for the electrophotographic photoreceptor 11 may be laid out at a position where it can be used together, and the same may be used on the primary receptor 20. The unit 15 may be provided. A conventional wet developer carrier is used for the pre-bath and the rinse liquid.

Next, after images of four colors are formed on the photoconductor 11, a predetermined preheating is performed by the preheating means 16 for thermal transfer of the photoconductor drum, and if necessary, further transfer on the primary receptor 20. The layer 22 is also subjected to predetermined preheating by using the preheating means 16, and the toner image on the surface of the photoconductor 11 is pressure-contacted onto the transfer layer 22 on the primary receptor 20 to be thermally transferred. The preheating means 16 is preferably a non-contact type infrared line heater or flash heater, and
The heating surface temperature of the photosensitive layer at the time of thermal transfer is preferably 40 to 150 ° C, particularly preferably 50 to 120 ° C. The nip pressure of these rollers is 0.2 to 20 kgf / cm ² , more preferably 0.5.
Although not shown in the figure, a spring or an air cylinder using compressed air at both ends of the roller shaft can be used as the roller pressing means although the pressure is up to 15 kgf / cm ² . The transport speed is 0.1 to 100 mm / sec, more preferably 0.5 to 50 mm / sec.

Then, the toner image completely transferred onto the primary receptor 20 is pressed against the final transfer material (coated paper etc.) 30 together with the transfer layer 22 to perform thermal transfer. The pre-heating means 16 of the primary receptor 20 performs a predetermined pre-heating, and the final transfer material 30 is subjected to a predetermined pre-heating by a transfer backup roller 31 and is pressed against the transfer layer 22 on which the toner image is formed on the primary receptor 20. After thermal transfer, the toner image is peeled and transferred together with the transfer layer 22 on the transfer material 30 while being cooled by the peeling back roller 32, and a series of steps is completed. Alternatively, as shown in FIG. 3, the primary receptor 20
However, an endless belt system may be used. Further, by stopping the apparatus with the transfer layer 22 formed on the primary receptor 20, the electrophotographic process can be started immediately when the next apparatus is operated.

In the color image forming method of the present invention, the conditions for transferring the toner image and the transfer layer are set as follows: the photoconductor (photosensitive layer and support) used, the physical properties of the primary receptor surface, the transfer layer, and It is natural to optimize the physical properties of the material such as the material to be transferred. In particular, the temperature conditions in the thermal transfer process include the glass transition point of the transfer layer, the softening temperature, the fluidity,
It is necessary to take into consideration factors such as adhesiveness, film formability, and film thickness. That is, the transfer layer, which has been softened to some extent by the preheating means, passes under the heating roller to increase the tackiness and adhere to the material to be transferred. Then, after passing under the cooling roller, the conditions should be set so that the temperature is lowered, the fluidity and the tackiness are reduced, and the toner as a film is peeled off while being adhered to the transfer layer together with the toner.

The material of the cooling roller is, for example, a heat conductive metal such as aluminum or copper coated with silicone rubber,
It is desirable to radiate heat by using a cooling means inside the roller or on the outer peripheral portion that does not contact the transfer paper. It is preferable to use a cooling fan, a cooling medium circulation device, an electronic cooling element, or the like as the cooling means, and to keep it in a predetermined temperature range in combination with a temperature controller.

As the transfer layer forming device 21 on another primary receptor, a melt coating device or a transfer device can be used instead of the electrodeposition coating method.
As the melt coating method, for example, a thermoplastic resin is applied to the surface of the primary receptor, for example, on the circumferential surface of the drum by a hot melt coater, and is cooled to a predetermined temperature by passing under a suction / exhaust unit to form a transfer layer. be able to. After that, it is preferable to move the hot melt coater to the standby position.

Further, as an apparatus for easily forming a transfer layer using a release paper in the transfer method on the primary receptor, for example, the apparatus shown in the schematic view of FIG. 4 can be mentioned. The release paper 24 provided with the transfer layer 22 is heated and pressed by the heating roller 25b to transfer the transfer layer to the surface of the primary receptor 20. The release paper 24 is cooled by the cooling roller 25c and collected. If necessary, the primary receptor 2
0 itself may be heated by the preheating means 25a to improve the transferability of the transfer layer 22 by thermocompression bonding.

In 120 parts of FIG. 4, after transferring the transfer layer 22 onto the primary receptor 20 by the release paper 24,
The portion 120 may be replaced with the portion 130 having the final transfer material 30 shown in FIG. 2 or 3, and the same transfer method may be used. Alternatively, the transfer layer 22 may be transferred onto the primary receptor 20 by the release paper 24. It is also possible to incorporate both the 120 part for transferring the toner image and the 130 part for transferring the transfer layer 22 on which the toner image is transferred to the final transfer material 30 in the apparatus. The transfer conditions for transferring the transfer layer 22 to the surface of the primary receptor 20 by the release paper 24 are preferably as follows.
The roller nip pressure is 0.1 to 10 kgf / cm ² , more preferably 0.2 to 8 kgf / cm ² , and the temperature during transfer is 2
It is 5 to 100 ° C, more preferably 40 to 80 ° C. Transport speed is 0.5 to 100 mm / sec, more preferably 3
˜50 mm / sec, which may be different in each of the transfer layer forming step, the electrophotographic step, and the thermal transfer step to the material to be transferred.

[0181]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

[Synthesis Example of Transfer Layer Resin Particles (AR)] Thermoplastic Resin Particles (AR) Synthesis Example 1: (AR-1) 10 g of dispersion stabilizing resin (Q-1) having the following structure, vinyl acetate
A mixed solution of 100 g and 384 g of Isopar H was heated to 70 ° C. with stirring under a nitrogen stream. 2,2 'as polymerization initiator
-Azobis (isovaleronitrile) (abbreviation AIVN) 0.8 g
Was added and reacted for 3 hours. Twenty minutes after the addition of the initiator, white turbidity occurred and the reaction temperature rose to 88 ° C. Further, 0.5 g of the initiator was added and after reacting for 2 hours, the temperature was raised to 100 ° C. and stirred for 2 hours to distill off unreacted vinyl acetate. After cooling 20
The white dispersion obtained through a 0-mesh nylon cloth was a latex having a polymerization rate of 90% and an average particle size of 0.23 μm and good monodispersity. The particle size is CAPA-500 (Horiba Ltd.)
Manufactured). A part of the white dispersion was subjected to a centrifuge (rotation speed 1 × 10 ⁴ rpm, rotation time 60 minutes) to collect the precipitated resin particles, and dried to obtain a weight average molecular weight (Mw) of the resin particles. And the glass transition point (Tg) were measured, Mw was 2 × 10 ⁵ (polystyrene-converted GPC value),
Tg was 38 ° C.

[0183]

[Chemical 12]

Synthesis Example 2 of thermoplastic resin particles (AR):
(AR-2) 15 g of dispersion stabilizing resin (Q-2) having the following structure, 75 g of benzyl methacrylate, 25 g of methyl acrylate, 1.3 g of methyl 3-mercaptopropionate and 552 g of Isopar H.
The mixed solution of was heated to a temperature of 50 ° C. with stirring under a nitrogen stream. 1 g of 2,2'-azobis (2-cyclopropylpropionitrile) (abbreviation ACPP) was added as a polymerization initiator, and the reaction was carried out for 2 hours. After further adding 0.8 g of ACPP and reacting for 2 hours, 0.8 g of AIVN initiator was added, and then the reaction temperature was 75 ° C.
The reaction time was 3 hours. Then, the mixture was heated to a temperature of 90 ° C., the unreacted monomer was distilled off under a reduced pressure of 20 to 30 mmHg and then cooled, and the white dispersion obtained through a 200-mesh nylon cloth had an average polymerization rate of 98%. The latex had a particle size of 0.20 μm and good monodispersity. The Mw of the resin particles is 2.
8 × 10 ⁴ , Tg was 55 ° C.

[0185]

[Chemical 13]

Synthesis Example 3 of thermoplastic resin particles (AR):
(AR-3) A mixed solution of 14 g of a dispersion stabilizing resin (Q-3) having the following structure and 382 g of Isopar G was stirred under a nitrogen stream at a temperature of 50.
Warmed to ° C. A mixture of 80 g of benzyl methacrylate, 20 g of vinyltoluene and 0.8 g of ACPP was added dropwise thereto for 1 hour, and the reaction was continued for another 1 hour. Further
Add 0.8g ACPP and react for 2 hours, then start AIV
Add 0.8 g of N. and heat to 80 ℃ for 2 hours, then AIV
N. 0.5g was added and reaction was performed for 2 hours. Then the temperature 10
The mixture was heated to 0 ° C, the unreacted monomer was distilled off under a reduced pressure of 10 to 20 mmHg, and then cooled. The white dispersion obtained through a 200-mesh nylon cloth had a polymerization rate of 90% and an average particle size of 0.17. It was a latex with a good monodispersity of μm. The Mw of the resin particles was 1 × 10 ⁵ , and the Tg was 55 ° C.

[0187]

[Chemical 14]

Synthesis Example 4 of thermoplastic resin particles (AR):
(AR-4) 14 g of dispersion stabilizing resin (Q-4) having the following structure, 10 g of dimethylsiloxane macromonomer (M-1) (FM-0725, manufactured by Chisso Corporation, Mw: 1 × 10 ⁴ ) and Isopar H 553
The mixed solution of g was heated to a temperature of 50 ° C. while stirring under a nitrogen stream. A mixture of 70 g of methyl methacrylate, 20 g of ethyl acrylate, 1.3 g of methyl 3-mercaptopropionate and 1.0 g of ACPP was added dropwise at a dropping time of 30 minutes, and the reaction was continued for another 1.5 hours. Add ACPP 0.8g and react for 2 hours, then add initiator AIVN 0.8g and set the temperature to 80 ℃ for 2 hours, then add ACPP 0.5g and continue for 2 hours.
The reaction was carried out over time. After cooling, the white dispersion obtained through a 200-mesh nylon cloth had a polymerization rate of 99% and an average particle size of
The latex was 0.15 μm with good monodispersity. Also,
The resin particles had Mw of 3 × 10 ⁴ and Tg of 50 ° C.

[0189]

[Chemical 15]

Synthesis Examples 5 of Thermoplastic Resin Particles (AR)
9: (AR-5) to (AR-9) In Synthesis Example 4 of the thermoplastic resin particles (AR), 10 g of the macromonomer (M-1) was used instead of each macromonomer described in Table-B. The resin particles (AR-5) to (AR-9) were manufactured in the same manner as in Synthesis Example 4 except for the above. The degree of polymerization of the obtained particles was 98 to 99%, the average particle size was in the range of 0.15 to 0.25 μm, the particle size distribution of the particles was narrow, and the monodispersibility was good. The Mw of the resin particles is
The glass transition point was 2.5 × 10 ⁴ to 4 × 10 ⁴ , and the glass transition point was in the range of 40 ° C. to 70 ° C.

[0191]

[Table 2]

Synthesis Example 10 of thermoplastic resin particles (AR):
(AR-10) Solid content of styrene-butadiene copolymer [(48/52) weight ratio] (Sorprene 303: manufactured by Asahi Kasei Co., Ltd.) having a softening point of 45 ° C. as a thermoplastic resin (A) is pulverizer trio blender 5g of coarsely crushed product, dispersion stabilizing resin: Sorprene 1205
(Asahi Kasei Co., Ltd.) 4 g and Isopar H51 g were placed in a paint shaker (manufactured by Toyo Seiki Co., Ltd.) having glass beads with a diameter of about 4 mm as a media and preliminarily dispersed for 20 minutes.
This preliminary dispersion was wet-dispersed at 4500 rpm for 6 hours using a Dynomill KDL type (manufactured by Shinmaru Enterprises Co., Ltd.) in which glass beads having a diameter of 0.75 to 1 mm were used as media. A white dispersion obtained by passing these through a 200-mesh nylon cloth was a latex having an average particle size of 0.4 μm.

Synthesis Examples 11 to 1 of Thermoplastic Resin Particles (AR)
6: (AR-11) to (AR-16) In Synthesis Example 10 of thermoplastic resin particles (AR), each compound of the following Table-C was used instead of the thermoplastic resin (A): Sorprene 303. A dispersion was prepared by the same wet dispersion method as in Synthesis Example 10. White dispersion has an average particle size of 0.3-0.6
It is in the range of μm and the softening point of the obtained resin particles is 40 ° C.
It was in the range of ~ 100 ° C.

[0194]

[Table 3]

Synthesis Example 17 of thermoplastic resin particles (AR):
(AR-17) A mixed solution of 18 g of a dispersion-stabilizing resin (Q-5) having the following structure and Isopar H 553 g was stirred at a temperature of 55 under a nitrogen stream.
Warmed to ° C. To this, a mixture of 60 g of methyl methacrylate, 40 g of methyl acrylate, 1.3 g of methyl 3-mercaptopropionate and 1.0 g of ACPP was added dropwise at a dropping time of 30 minutes, and the reaction was continued for another 1.5 hours. Further ACPP 0.
8 g was added and reacted for 2 hours, then 0.8 g of AIVN initiator was added and the temperature was set to 80 ° C. for 2 hours, and 0.5 g of ACPP was further added and reacted for 2 hours. After cooling, the white dispersion obtained through a 200-mesh nylon cloth was a latex having a polymerization rate of 99% and an average particle size of 0.15 μm and good monodispersity. The Mw of the resin particles was 1.5 × 10 ⁴ , and the Tg was 45 ° C.

[0196]

[Chemical 16]

Synthesis Example 18 of thermoplastic resin particles (AR):
(AR-18) A mixture of 12 g of the dispersion stabilizing resin (Q-1), 70 g of vinyl acetate, 30 g of vinyl butyrate and 388 g of Isopar H was heated to a temperature of 80 ° C. with stirring under a nitrogen stream. In addition to this, azobisisobutyronitrile (abbreviation: AIBN) was used as an initiator.
1.5 g was added and the reaction was carried out for 2 hours, and 0.8 g of AIBN was added twice every 2 hours to carry out the reaction. After cooling, the white dispersion obtained through a 200 mesh nylon cloth had a polymerization rate of 93%.
It was a latex having an average particle size of 0.18 μm and good monodispersity. The resin particles had Mw of 8 × 10 ⁴ and Tg of 18 ° C.

Synthesis Example 19 of thermoplastic resin particles (AR):
(AR-19) 18 g of dispersion stabilizing resin (Q-3) and 549 g of Isopar H
The mixture was heated to 55 ° C with stirring under a nitrogen stream. To this, 70 g of benzyl methacrylate, 30 g of methyl acrylate, and 2.6 of methyl 3-mercaptopropionate.
g and AIVN 1.0 g were added dropwise at a dropping time of 1 hour, and the reaction was continued for another 1 hour. After adding AIVN 0.8g, set the temperature to 75 ° C for 2 hours, then AIVN 0.8g
Was added and reacted for 3 hours. After cooling, the white dispersion obtained through a 200 mesh nylon cloth had a polymerization rate of 98%.
It was a latex having an average particle size of 0.18 μm and good monodispersity. The resin particles had Mw of 3 × 10 ⁴ and Tg of 18 ° C.

Synthesis Examples 20 to 2 of thermoplastic resin particles (AR)
9: (AR-20) to (AR-29) In Synthesis Example 19 of thermoplastic resin particles (AR), each monomer shown in Table D below was used instead of 70 g of benzyl methacrylate and 30 g of methyl acrylate. Others were the same as in Synthesis Example 19 to produce resin particles (AR). The degree of polymerization of each of the obtained white dispersions was 90 to 99%, and the average particle size was 0.13 to 0.20 μm, which was a latex having good monodispersity. The Tg of each resin particle was in the range of 10 ° C to 25 ° C.

[0200]

[Table 4]

Synthesis Example of Resin Particles (ARW) 1: (ARW
-1) According to Synthesis Example 18 of resin particles (AR), resin particles (AR
-18) was synthesized. A mixed solution of the resin particle dispersion (that is, seed particles) and 10 g of the dispersion stabilizing resin (Q-5) was heated to a temperature of 60 ° C. with stirring under a nitrogen stream. 60g of methyl methacrylate, 40 of methyl acrylate
g, methyl 3-mercaptopropionate 2.0 g, AIVN
A mixture of 0.8 g and 400 g of Isopar G was added dropwise over 2 hours, and the reaction was continued for another 2 hours. Then 0.8 g of initiator
Add the mixture to 70 ℃ and react for 2 hours.
The reaction was continued for 3 hours. After cooling, it was passed through a 200-mesh nylon cloth, and the resulting white dispersion had a polymerization rate of 98% and an average particle size of 0.
The latex was 25 μm and had good monodispersity.

Next, whether or not the obtained resin particles were formed as individual particles was examined by observing the state of the particles using a scanning electron microscope (SEM). A film prepared by making resin particles dispersed on a PET film was heat-treated at a temperature of 50 ° C. and 80 ° C. for 5 minutes, and then each sample was processed by JEOL, JSL-T330 type Sca.
When observed at 20,000 times using the nning Microscope, the temperature
Particles were observed in the sample at 50 ° C, but no particles were observed at 80 ° C. That is, the particles were melted by heating. Similarly, resin particles (AR-17) each consisting of two kinds of resins (copolymers) constituting the particles of the present invention (AR-17)
(Tg 45 ° C.) and resin particles (AR-18) (Tg 18 ° C.), and dispersed resin particles obtained by mixing these two kinds of particles at a 1/1 weight ratio were examined. The sample containing the resin particles (AR-18) was not heated, but the sample was in a particle state, but at a temperature of 50 ° C., the particle state was not observed, and the resin particles (AR-1) were not observed.
In the sample of 7), particles disappeared at a temperature of 80 ° C. Further, when a sample made up of mixed particles and a sample not heated and a temperature of 50 ° C. were examined, it was confirmed that particles were not visible in the sample having a temperature of 50 ° C. as compared with the unheated sample.

As described above, as a result of visual observation of the heat-raising of the particles, the resin particles synthesized according to the examples of the present invention were not a mixture of two kinds of resin particles but two particles in one particle. Cores in which a high Tg resin is distributed in the outer layer and a low Tg resin is distributed in the inner layer.
It was confirmed to be shell particles. The resin particles of the present invention are composed of a resin having a high Tg (AH) and a resin having a low Tg (AH).
L) may be any of the core-shell structure having the above-mentioned constitution, the core-shell structure of the reverse combination, and the particles present without being unevenly distributed, and is not particularly limited.

Synthesis Examples 2-8 of Resin Particles (ARW): (A
RW-2) to (ARW-8) In Synthesis Example 1 of the above resin particles (ARW), the following table-
Particles (ARW-2) to (ARW) of the present invention were operated in exactly the same manner as in Synthesis Example 1 except that each monomer described in E was used.
-8) was produced. The degree of polymerization of each latex particle obtained was 95 to 99%, the average particle diameter was in the range of 0.20 to 0.30 μm, and the monodispersity was good.

[0205]

[Table 5]

Synthesis Example 9 of Resin Particles (ARW): (ARW)
-9) As the resin (A), a Tg-25 ° C [vinyl acetate / ethylene [46/54 weight ratio] copolymer (Evaflex 45X:
Mitsui DuPont Chemical Co., Ltd.) and polyvinyl acetate having a Tg of 38 ° C. at a ratio of (1/1) by weight are used and the temperature is 12
The mixture was melt-kneaded with a three-roll mill at 0 ° C. This kneaded product was roughly crushed with a crusher trio blender, and 5 g of this crushed product, 4 g of dispersion stabilizing resin: Sorprene 1205 (manufactured by Asahi Kasei Corporation)
Further, 51 g of Isopar H was charged into a paint shaker (manufactured by Toyo Seiki Co., Ltd.) using glass beads having a diameter of about 4 mm as a media and preliminarily dispersed for 20 minutes. This predispersion is
Dyno Mill K with 0.75 ~ 1 mm glass beads as media
Using DL type (manufactured by Shinmaru Enterprises Co., Ltd.), wet dispersion was performed at 4500 rpm for 6 hours. A white dispersion obtained by passing these through a 200-mesh nylon cloth was a latex having an average particle size of 0.4 μm.

Synthesis Examples of Resin Particles (ARW) 10 to 14: (A
RW-10) to (ARW-14) In the same manner as in Synthesis Example 9 except that each compound of the following Table-F was used in place of the two kinds of resin (A) used in Synthesis Example 9 of resin particles (ARW). A dispersion was prepared by the same wet dispersion method. The white dispersion had an average particle size in the range of 0.3 to 0.6 μm.

[0208]

[Table 6]

[Synthesis Example of Binder Resin (P)] Synthesis Example 1: Resin (P) 1: (P-1) 80 g of methyl methacrylate, the macromonomer (M-
1) A mixed solution of 20 g and 200 g of toluene was heated to a temperature of 75 ° C under a nitrogen stream. AIBN (1.0 g) was added and reacted for 4 hours, and AIBN (0.7 g) was further added and reacted for 4 hours.
The Mw of the obtained copolymer was 5.8 × 10 ⁴ (measured by GPC method).

[0210]

[Chemical 17]

Synthesis Examples 2 to 9 of Resin (P): (P-2) to
(P-9) In Synthesis Example 1 of Resin (P), instead of methyl methacrylate and macromonomer (M-1), the following Table-G was used.
Other than using each monomer corresponding to the polymer component described in,
Each polymer was synthesized in the same manner as in Synthesis Example 1. The Mw of each polymer obtained was in the range of 4.5 × 10 ^{4 to} 6 × 10 ⁴ .

[0212]

[Table 7]

[0213]

[Table 8]

Synthesis Example 10 of Resin (P): (P-10) 2,2,3,4,4,4-hexafluorobutylmethacrylate 60
g, macromonomer of methyl methacrylate (AA-
6) A mixed solution of 40 g of Mw1 × 10 ⁴ manufactured by Toagosei Kagaku Co., Ltd. and 200 g of benzotrifluoride was placed under a nitrogen stream at a temperature of 75 ° C.
Warmed to. AIBN (1.0 g) was added and reacted for 4 hours, and 1.IBN (0.5 g) was further added and reacted for 4 hours. The Mw of the obtained copolymer was 6.5 × 10 ⁴ .

[0215]

[Chemical 18]

Synthesis Examples 11 to 15 of Resin (P): (P-11) to
(P-15) Instead of the monomer and macromonomer used in Synthesis Example 10 of resin (P), each monomer and each macromonomer corresponding to the polymer components shown in Table 1H below were used. The other is
Each copolymer was synthesized in the same manner as in Synthesis Example 10. The Mw of the obtained copolymer was in the range of 4.5 × 10 ^{4 to} 6.5 × 10 ⁴ .

[0217]

[Table 9]

[0218]

[Table 10]

[0219]

[Table 11]

Synthesis Example 16 of Resin (P): (P-16) 67 g of methyl methacrylate, 22 g of methyl acrylate,
A mixed solution of 1 g of methacrylic acid and 200 g of toluene was heated to a temperature of 80 ° C under a nitrogen stream. To this, 10 g of a polymeric azobis initiator (PI-1) having the following structure was added and reacted for 8 hours. After completion of the reaction, reprecipitation in 1.5 liter of methanol,
The obtained precipitate was collected and dried, and the yield was 75 g, and the Mw was 3 ×.
10 ⁴ copolymers were obtained.

[0221]

[Chemical 19]

Synthesis Example 17 of Resin (P): (P-17) 70 g of methyl methacrylate and 200 g of tetrahydrofuran
The mixed solution of 1 was thoroughly degassed under a nitrogen stream and cooled to -20 ° C. 0.8 g of 1,1-diphenylbutyllithium was added and reacted for 12 hours. Furthermore, the following monomer (m-
1) A mixed solution of 30 g and 60 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream and added, and the mixture was further reacted for 8 hours. After this mixture was heated to 0 ° C, 10 ml of methanol was added.
After reacting for 30 minutes, the polymerization was stopped. The obtained polymer solution was heated to a temperature of 30 ° C. with stirring, 3 ml of 30% hydrogen chloride ethanol solution was added thereto, and the mixture was stirred for 1 hour. Then, the solvent was distilled off under reduced pressure until the total amount became half,
Reprecipitated in 1 liter of petroleum ether. The precipitate was collected and dried under reduced pressure to obtain a polymer having an Mw of 6.8 × 10 ⁴ and a yield of 76 g.

[0223]

[Chemical 20]

Synthesis Example 18 of Resin (P): (P-18) Methyl methacrylate 52.5 g, methyl acrylate 22.5
A mixed solution of g, 0.5 g of (tetraphenylporphinato) aluminum methyl and 200 g of methylene chloride was heated to 30 ° C. under a nitrogen stream. This is irradiated with 300 W-xenon lamp light through a glass filter from a distance of 25 cm, and 20
Reacted for hours. This mixture was further mixed with the following monomer (m-
2) After adding 25 g and irradiating for 12 hours in the same manner, 3 g of methanol was added to this reaction mixture and stirred for 30 minutes to stop the reaction. The reaction mixture was then reprecipitated in 1.5 liters of methanol, the precipitate was collected and dried. The yield of the obtained polymer was 78 g, and the Mw was 7 × 10 ⁴ .

[0225]

[Chemical 21]

Synthesis Example 19 of Resin (P): (P-19) Ethyl Methacrylate 50 g, Glycidyl Methacrylate
10 g and benzyl N, N-diethyldithiocarbamate 4.
8 g of the mixture was sealed in a container under a nitrogen stream and heated to a temperature of 50 g. This was irradiated with light from a high pressure mercury lamp of 400 W at a distance of 10 cm from a glass filter for 6 hours for photopolymerization. This was dissolved in 100 g of tetrahydrofuran, 40 g of the following monomer (m-3) was added, the atmosphere was replaced with nitrogen, and the amount was again 10
Irradiated for hours. The obtained reaction product was reprecipitated in 1 liter of methanol, collected, and dried. The polymer obtained has a yield of 73.
The Mw was 4.8 × 10 ⁴ in g.

[0227]

[Chemical formula 22]

Synthesis Example 20 of Resin (P): (P-20) Methyl Methacrylate 50 g, Ethyl Methacrylate 25 g
And a mixture of benzyl isopropyl xanthate 1.0 g,
The container was sealed under a nitrogen stream and heated to a temperature of 50 ° C. This was irradiated with light from a high pressure mercury lamp of 400 W from a distance of 10 cm through a glass filter for 6 hours to perform photopolymerization. To this, 25 g of the monomer (m-1) was added, and the atmosphere was replaced with nitrogen, and light was again irradiated for 10 hours. The obtained reaction product was reprecipitated in 2 liters of methanol, collected, and dried to obtain a polymer having a yield of 63 g and a Mw of 6 × 10 6.
^{Was 4} .

[0229]

[Chemical formula 23]

Synthesis Examples 21-27 of Resin (P): (P-21)-
(P-27) In the same manner as in Synthesis Example 19 of Resin (P), each copolymer shown in Table I below was synthesized. The Mw of the obtained polymer was 3.5 × 10 ⁴ to
The range was 6 × 10 ⁴ .

[0231]

[Table 12]

[0232]

[Table 13]

Synthesis Example 28 of Resin (P): (P-28) In Synthesis Example 19 of Resin (P), 18 g of an initiator (I-11) having the following structure was used instead of benzyl N, N-diethyldithiocarbamate. Was synthesized in the same manner as in Synthesis Example 19 except that
A copolymer having an Mw of 4.5 × 10 ⁴ was obtained.

[0234]

[Chemical formula 24]

Synthesis Example 29 of Resin (P): (P-29) In Synthesis Example 20 of Resin (P), 0.8 g of an initiator (I-12) having the following structure was used instead of benzyl isopropyl xanthate.
Except for using
A copolymer of 0 ⁴ was obtained.

[0236]

[Chemical 25]

Synthesis Example 30 of Resin (P): (P-30) Methyl Methacrylate 68 g, Methyl Acrylate 22 g,
A mixed solution of 10 g of glycidyl methacrylate, 17.5 g of an initiator (I-13) having the following structure, and 150 g of tetrahydrofuran was heated to a temperature of 50 ° C under a nitrogen stream. 400W for this solution
Photopolymerization was carried out by irradiating with light from a high pressure mercury lamp at a distance of 10 cm through a glass filter for 10 hours. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried,
A polymer having an Mw of 4.0 × 10 ⁴ was obtained with a yield of 72 g. This polymer 70
g, monomer (M-2) 30 g and tetrahydrofuran 100 g
The mixed solution of was heated to a temperature of 50 ° C. under a nitrogen stream, and was irradiated with light under the same conditions as above for 13 hours. The reaction is then methanol 1.
Re-precipitate in 5 liters and collect and dry the precipitate to obtain a yield of 78
A copolymer having an Mw of 6 × 10 ⁴ was obtained in g.

[0238]

[Chemical formula 26]

Synthesis Examples 31-38 of Resin (P): (P-31)-
(P-38) In Synthesis Example 30 of Resin (P), the initiator (I-13) 17.5
The same operation as in Synthesis Example 30 was carried out except that 0.031 mol of the initiator (I) shown in Table J below was used instead of g. The yield of each polymer obtained was 70 to 80 g and had a Mw of ⁴ × 10 ^{4 to} 6 × 10 ^4.
Met.

[0240]

[Table 14]

[0241]

[Table 15]

[0242]

[Table 16]

[Synthesis Example of Resin Particles (L)] Synthesis Example 1: Resin Particles (L) 1: (L-1) 40 g of the monomer (LM-1) having the following structure, 2 g of ethylene glycol dimethacrylate, and the following structure A mixed solution of 4.0 g of the dispersion stabilizing resin (LP-1) and 180 g of methyl ethyl ketone was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. AI
0.3 g of VN was added and reacted for 3 hours. In addition, AIVN 0.1
g was added and reacted for 4 hours. After cooling, a white dispersion was obtained through a 20-mesh nylon cloth, which was a latex having an average particle size of 0.25 μm (particle size was measured by CAPA-500 (manufactured by Horiba, Ltd.)).

[0244]

[Chemical 27]

Synthesis Example 2 of Resin Particles (L): (L-2) As a dispersion stabilizing resin (AB-6) (Toa Gosei Co., Ltd.)
Production: A mixed solution of 5 g of a monofunctional macromonomer consisting of butyl acrylate units) and 140 g of methyl ethyl ketone was heated to a temperature of 60 ° C. with stirring under a nitrogen stream. To this, a mixed solution of 40 g of a monomer (LM-2) having the following structure, 1.5 g of ethylene glycol diacrylate, 0.2 g of AIVN and 40 g of methyl ethyl ketone was added dropwise over 1 hour. After reacting for 2 hours as it was, 0.1 g of AIVN was further added and reacted for 3 hours to obtain a white dispersion. After cooling, the average particle size of the dispersion obtained through a 200-mesh nylon cloth is 0.35 μm
Met.

[0246]

[Chemical 28]

Synthesis Examples 3 to 11 of Resin Particles (L): (L-
3) to (L-11) In Synthesis Example 1 of the resin particles (L), the monomer (LM-
Resin particles were produced in the same manner as in Synthesis Example 1 except that 1), ethylene glycol dimethacrylate, and methyl ethyl ketone were replaced with the compounds shown in Table K below. The average particle diameter of the obtained resin particles was in the range of 0.15 to 0.30 μm.

[0248]

[Table 17]

[0249]

[Table 18]

Synthesis Examples 12 to 17 of Resin Particles (L): (L-1
2) to (L-17) In Synthesis Example 2 of resin particles (L), 5 g of the dispersion stabilizing resin (AB-6) is used instead of the resin (LP) shown in Table L below.
Each resin particle was synthesized in the same manner as in Synthesis Example 2 except that The average particle size of the obtained particles was in the range of 0.10 to 0.25 μm.

[0251]

[Table 19]

[0252]

[Table 20]

Synthesis Examples 18 to 23 of Resin Particles (L): (L-1
8) to (L-23) In Synthesis Example 2 of resin particles (L), the monomer (LM-
2) Instead of 40 g, each monomer of the following Table-M was used, and instead of 5 g of the dispersion stabilizing resin (AB-6), the resin of the following structure (L
P-8) was used in the same manner as in Synthesis Example 2 except that 6 g was used,
Each resin particle was synthesized. The average particle size of the obtained particles is 0.
It was in the range of 05 to 0.20 μm.

[0254]

[Chemical 29]

[0255]

[Table 21]

[0256]

[Table 22]

Example 1 X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) 2
g, 10 g of a binder resin (B-1) having the following structure, the resin (P
-1) A mixture of 0.3 g, 0.15 g of the compound (A) having the following structure and 80 g of tetrahydrofuran was put in a 500 ml glass container together with glass beads, and dispersed for 60 minutes with a paint shaker (manufactured by Toyo Seiki Seisakusho Co., Ltd.). Phthalic acid 0.
After 03 g and 0.01 g of phthalic acid were added and dispersed for 2 minutes, the glass beads were filtered to obtain a photosensitive layer dispersion liquid.

[0258]

[Chemical 30]

Then, this dispersion was coated on a 0.2 mm thick base paper for a master for a printing plate with a wire bar, dried by touch with a finger, and then dried in a circulating oven at 120 ° C. for 2 minutes. Heated for hours. The thickness of the obtained photoreceptor is 8
was μm. The adhesive strength of the surface of the photoconductor according to JIS Z 0237-1980 "Test method for adhesive tape / adhesive sheet" was 3 g · f. On the other hand, in the photosensitive layer, the resin (P-1) 0.
Except for 3 g, the surface of the photosensitive member formed in the same manner as the photosensitive layer had an adhesive force of 450 g · f or more and showed no peeling property.

The above-mentioned photoconductor having an easily peelable surface was mounted as the electrophotographic photoconductor 11 in the apparatus shown in FIG. Further, in the apparatus of FIG. 2, as a primary receptor 20, a blanket 9600-A for offset printing (adhesive force 80 g
(F, overall thickness 1.6 mm, made by Meiji Rubber), a dispersion (L-1) of resin (A) having the following contents was supplied to a wet electrodeposition unit 21 which is a transfer layer type device, The transfer layer 22 was formed by a wet electrodeposition method.

Resin (A) dispersion [L-1] Resin (A) dispersion: (AR-4) 5 g (as solid content) Resin (A) dispersion: (AR-18) 5 g (As solid content) Charge control compound (D-1) 0.03 g (octadecyl vinyl ether / t-octyl maleic acid half amide) copolymer Silicon oil (KF-96) 5 g (manufactured by Shin-Etsu Silicone Co., Ltd.) Was adjusted to 1 liter with Isopar H.

The peripheral velocity of the primary receptor 20 was rotated at 10 mm / sec, and while supplying the dispersion liquid to the surface of the primary receptor using a slit electrodeposition device, the primary receptor side was grounded and the electrode side of the slit electrodeposition device was- A voltage of 250 V was applied to electrodeposit the resin particles. Then, the dispersion liquid was removed by air squeeze using an intake / exhaust unit to form a thermoplastic resin transfer layer 22 by melting and filming with an infrared line heater as a preheating means. The film thickness at this time was 5 μm.

Next, an electrophotographic process was performed. Pass the photoconductor 11 under the corona charging device 18 in the dark,
After the corona charging to + 450V, the original was read by a color scanner in advance, color separation was performed, and some corrections related to the color reproduction unique to the system were added, and then stored in the hard disk in the system as digital image data. Based on the information about yellow among the colors of yellow, magenta, cyan, and black, in the negative image mode, using the semiconductor laser drawing device 19, the exposure amount on the photoconductor is 30 erg / cm ² with 788 nm light. Exposed.

Subsequently, the positively charged yellow toner for the signature system (manufactured by Kodak) is 75 times as much as Isopar H.
It is diluted with (made by Esso Standard Petroleum) and supplied to the yellow liquid developing unit 14Y, a bias voltage of + 350V is applied to the developing unit 14Y side, and reversal development is performed so that toner is electrodeposited on the exposed portion, and then isoparation is performed. After rinsing in the H-only bath to remove stains on the non-image area,
It was passed under the intake / exhaust unit 15 and the preheating means 16 to be dried. The above toner development processing is performed with magenta (14M),
After obtaining color toner images by repeating each of cyan (14C) and black (14K), the surface temperature of the photoconductor is 60.
It heated using the preheating means 16 and the temperature control means 17 so that it might become (degreeC).

Next, the photoconductor 11 drum and the primary receptor 20 whose surface temperature was set to 110 ° C. by the temperature adjusting means 17
When the drum was brought into contact and heated and pressed under conditions of a nip pressure of 5 kgf / cm ² and a drum peripheral speed of 5 mm / sec, the color toner image was completely transferred to the transfer layer 22 on the primary receptor 20. Next, the surface temperature is adjusted to 60 by the temperature adjusting means 17.
20 drums of primary receptor set at ℃, backup roller 31 and 10 ℃ for transfer set at 130 ℃
Between the backup roller 32 for peeling set to
Guide the coated paper that is the final printing material 30 that is the final printing material,
With nip pressure of 5 kgf / cm ² and drum peripheral speed of 10 mm / sec,
When heating and pressing were performed, the color toner image was completely transferred onto the coated paper 30, and a high-quality and clear color image was obtained.

On the other hand, the transfer layer 2 is formed on the primary receptor 20.
A color image was formed on the coated paper 30 by a method of transferring without providing No. 2, and compared with the present invention. The color image of the obtained coated paper was found to have a missing toner image or uneven image density. Further, visual inspection of fine lines, fine characters, and the like with a 20-fold loupe revealed that a fine image was missing. Further, when the surface of the photoconductor was observed, residual toner image areas were observed. This means that in the method of repeatedly using the photoconductor, cleaning of the photoconductor surface to remove the residual toner, installation of an apparatus for that purpose, or damage to the photoconductor surface due to cleaning or the like becomes a problem. On the other hand, in the present invention, the peeling of the toner image from the photoconductor is sufficiently performed by using the resin layer as the transfer layer, and the toner image is easily and sufficiently transferred from the primary receptor to the final transfer material. It can be seen that the toner image is preferably protected by the transfer layer.

Example 2 Amorphous silicon was used as the electrophotographic photosensitive member 11 and the electrophotographic photosensitive member 11 was mounted in the apparatus shown in FIG. To impart releasability to the surface of the photoconductor 11, the photoconductor is brought into contact with a solution in which 1 g of a releasable compound (S-1) (polyether-modified silicone oil) having the following structure is dissolved in 1 liter of Isopar G, Lap speed 30
After rotating for 10 seconds at a rotation speed of mm / sec, squeezing was performed with a squeeze roll, and then dried by a preheating means 16. As a result, the photoreceptor having an adhesive force of 203 g · f has an adhesive force of 8 g · f.

[0268]

[Chemical 31]

The transfer layer 22 on the primary receptor 20
As a thermoplastic resin, ethylene-vinyl acetate copolymer (vinyl acetate content 20% by weight, softening point 90 by ring and ball method)
℃) is applied to the surface of the primary receptor 20 at a speed of 20 mm / sec by a hot melt coater set at 120 ° C., and cooling air is blown from an intake / exhaust unit to cool.
The transfer layer 22 was formed. The thickness of the transfer layer 22 at this time is 2.
It was 5 μm. Next, the amorphous silicon photoconductor 11 having releasability is corona charged to + 700V in a dark place, and then read from a document by a color scanner in advance, and color separation is performed to correct some system-specific color reproduction. Of the colors of yellow, magenta, cyan, and black, which were stored in the hard disk in the system as digital image data, the semiconductor laser was used based on the information about yellow.
It was exposed to light of 780 nm. The potential of the exposed portion was + 220V and that of the unexposed portion was + 600V.

Next, after pre-bathing with Isopar H (made by Esso Standard Petroleum) by a pre-bath device incorporated in the developing unit, 50% of positively charged yellow toner for Versatech 3000 (color electrostatic plotter made by Xerox) is used. A wet developer diluted with twice the amount of Isopar H was supplied from the developing unit to the surface of the photoreceptor. At this time, a developing bias voltage of +500 V was applied to the developing unit side to carry out reversal development so that the toner was electrodeposited on the yellow unexposed portion. Then, rinsed in a bath of Isopar H alone to remove stains on the non-image area, and dried in an intake / exhaust unit. The above process was repeated for each color of magenta, cyan and black.

Next, the infrared line heater was turned on and passed underneath, and the surface temperature was measured by a radiation thermometer to about 80 ° C., after which the primary receptor (drum) 20 provided with the transfer layer 22 was provided. Is heated to a temperature of 100 ° C., the photoconductor 11 drum and the primary receptor 20 are brought into contact with each other, and the color toner image is entirely transferred onto the primary receptor 20 under the conditions of a nip pressure of 4 kgf / cm ² and a drum peripheral speed of 5 mm / sec. It was transcribed.
Next, the coated paper 30 and the color toner image 3 are transferred to the transfer layer 2
10kgf /
It was passed at a speed of 15 mm / sec under a heated rubber roller 31 whose surface temperature was controlled to 120 ° C. under the pressure of cm ² . After that, when the coated paper 30 was peeled off after being cooled by passing under the cooling roller 32,
The toner 3 of the primary receptor 20 was thermally transferred to the coated paper 30 side together with the transfer layer 22. Further, since the toner on the coated paper 30 was completely covered with the thermoplastic resin 22 as the transfer layer, it did not rub off.

Example 3 X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) 2
g, a mixture of 10 g of the binder resin (B-2) having the following structure, 0.15 g of the compound (B) having the following structure, and 80 g of tetrahydrofuran together with glass beads in a 500 ml glass container, and using a paint shaker (Toyo Seiki Seisakusho) After dispersing for 60 minutes, the glass beads were filtered to obtain a photosensitive layer dispersion liquid.

[0273]

[Chemical 32]

[0274] Then, this dispersion was applied onto a 0.2 mm thick base paper for a master for a printing plate, which had been subjected to a conductive treatment and a solvent resistance treatment, by a wire bar, and was dried by touching with a finger, and then in a 110 ° C circulating oven for 20 seconds. Heated. The film thickness was 8 μm. The above-mentioned photoreceptor is mounted on the apparatus shown in FIG. 3, and in the compound (S) coated portion 110, compound (S-2) having the following structure (carboxy-modified silicone oil TSF4770: Toshiba) is provided to impart releasability to the photoreceptor 11. Silicone Co., Ltd.) was contacted with a metalling roll having a silicone rubber layer on the outermost surface in contact with a bath containing oil, and both drums were rotated for 20 seconds at a peripheral speed of 15 mm / second. It was By this treatment, the adhesive force on the surface of the photoconductor became 5 g · f.

[0275]

[Chemical 33]

Also, the same result as above can be obtained by processing through a transfer roll having a styrene-butadiene rubber layer on the outermost surface between the metering roll immersed in the silicone oil bath and the photoconductor. It was

Further, in the method using the above-mentioned metering roll / transfer roll, the method of supplying the compound (S-2) 113 between the metering roll 112 and the transfer roll 111 as shown in FIG. Good results have been obtained.

Also, the transfer layer 2 on the primary receptor 20
2 was formed by transfer from the release paper shown in FIG. That is, as the release paper 24, a separate paper (Oji Paper Co., Ltd.)
Manufactured by K.K.), on which a paper having a film thickness of 3 μm composed of poly (vinyl acetate) and poly (phenethyl methacrylate) (5/5 weight ratio) was formed as a primary receptor Pressed against 20 and pressure between rollers 3kgf / c
A transfer layer 2 having a film thickness of 3 μm was formed on the surface of the primary receptor 20 under the conditions of m ² , surface temperature of 60 ° C. and passage speed of 10 mm / sec.
Formed 2. A color image was formed in the same manner as in Example 1 using the photoreceptor 11 and the primary receptor 20 having the transfer layer 22 formed thereon. The obtained color image on the coated paper 30 was a good image without fog, and the image strength was sufficient, as in Example 2.

Example 4 The transfer layer 22 on the primary receptor 20 in Example 1
A color image was formed in the same manner as in Example 1 except that the above-mentioned two-layer constitution was adopted. <Formation of transfer layer> First, using the following electrodeposition dispersion liquid, the primary receptor was charged to -150 V to electrodeposit resin particles, and the film thickness
A first layer of 2.5 μm was formed. Electrodeposition dispersion liquid of resin (A) Resin particles (AR-1) 10 g (as solid content) Compound (D-2) for charge control having the following structure 0.02 g Branched tetradecyl alcohol (FOC-1400) 8 g ( Nissan Chemical Co., Ltd.) was adjusted with Isopar G so that the total volume was 1.0 liter.

[0280]

[Chemical 34]

Next, the following electrodeposition dispersion liquid was used thereon,
After charging to -150 V, the resin particles were electrodeposited to form a second layer having a film thickness of 2 μm. -Electrodeposition dispersion of resin (A) In the above dispersion, the same procedure as in the first layer was performed except that 10 g of resin particles (AR-24) was used instead of 10 g of resin particles (AR-1). .

The color image on the obtained coated paper 30 is
There was no background fog and the image quality was clear, and it was a copied image. The strength of the image area was also sufficient. Furthermore, in the transfer image forming operation, the primary receptor 20 is removed from the photoreceptor 11.
The heat and pressure transfer conditions from the primary receptor 20 to the final transfer material 30 were manipulated to improve the low temperature transfer speed as described below. Primary receptor surface temperature: 80 ° C. Drum peripheral speed: 15 mm / sec The color image on coated paper obtained by operating under these conditions had no problem at all. In addition, no transfer layer remained on the surface of the primary receptor after transfer when transferred under these conditions.

Further, when a color image was prepared by using a commercially available copy paper for a copying machine in place of the coated paper which is the main printing paper as the final transfer material 30, almost no color image quality on the coated paper was obtained. A color image having no difference was obtained. That is, even if the paper quality of the final transfer material was changed, it was not affected and a good color copy was obtained.

Examples 5-14 In Example 1, 5 g of the resin particles (AR-4) and 5 g of (AR-18) in the dispersion liquid [L-1] of the resin (A) were replaced by those shown in the following Table-N. A color image was formed in the same manner as in Example 1 except that each resin particle (AR) was used.

[0285]

[Table 23]

The color copy thus obtained had a clear image quality without background stains. In other words, the toner image formed on the photoconductor has good image reproducibility and good image pick-up with no fog in the non-image area, and transfer of each transfer layer to coated paper Transferred completely without unevenness. Furthermore, even if you add or stamp on the copy paper,
The procedure was the same as for plain paper.

Examples 15 to 30 Transfer images were obtained in the same manner as in Example 2 except that the resins shown in Table 0 below were used in place of the ethylene-vinyl acetate copolymer used in the transfer layer. When the forming operation was performed, the same results as in Example 2 were obtained.

[0288]

[Table 24]

Examples 31 to 37 In Example 3, release paper instead of the separate paper provided with the transfer layer: Sun release (manufactured by Sanyo Kokusaku Pulp Co., Ltd.)
A color image was prepared in the same manner as in Example 3, except that a paper having a resin thickness of 3.5 μm and provided with each resin (A) shown in Table P below was used.

[0290]

[Table 25]

[0291]

[Table 26]

The obtained color image was a clear image without background fog, and almost no deterioration in image quality was recognized as compared with the original. This means that a transfer layer is formed on the primary receptor using release paper, and after the toner image is formed,
It has been shown that even by the method of transferring onto coated paper, the transfer layer at each transfer is uniformly and completely transferred, and no adverse effect on image deterioration occurs.

Example 38 5 g of 4,4'-bis (diethylamino) -2,2'-dimethyltriphenylmethane was used as an organic photoconductive substance.
4 g of a binder resin (B-3) having the following structure, the resin (P-2
7) 0.4 g, dye (D-1) 40 mg of the following structural formula and anilide compound (C) 0.2 g of the following structural formula as a chemical sensitizer,
It was dissolved in a mixture of 30 ml of methylene chloride and 30 ml of ethylene chloride to obtain a photosensitive layer dispersion liquid.

[0294]

[Chemical 35]

[0295]

[Chemical 36]

This photosensitive layer dispersion was applied onto a conductive transparent support (polyethylene terephthalate support having a thickness of 100 μm and a vapor deposition film of indium oxide, surface resistance 10 ³ Ω) using a wire round rod. Then about 4μ
An organic thin film having a photosensitive layer of m was obtained. The adhesive force on the surface of the photoconductor was 8 gf. A transfer image was formed in the same manner as in Example 1 except that this photosensitive member was used instead of the photosensitive member used in Example 1. The obtained color copied image of the coated paper after transfer was clear without background fog, and the image strength was good in durability.

Example 39 5 g of bisazo pigment having the following structure and 95 g of tetrahydrofuran
And polyester resin: Byron 200 (Toyobo Co., Ltd.)
5 g) was thoroughly ground in a ball mill. Then, this mixture was taken out, and 520 g of tetrahydrofuran was added with stirring. This dispersion was applied onto the conductive transparent support used in Example 38 using a wire round rod to form a charge generation layer having a thickness of about 0.7 μm.

[0298]

[Chemical 37]

Next, a hydrazone compound of the following structural formula 20
g, polycarbonate resin (GE company, trade name Lexan
121) A mixed solution of 20 g and tetrahydrofuran 160 g is applied on the charge generation layer using a wire round rod, dried at 60 ° C. for 30 seconds and further heated at 100 ° C. for 20 seconds to form a charge transport layer of about 18 μm. Was formed to obtain an electrophotographic photoreceptor having a photosensitive layer composed of two layers.

[0300]

[Chemical 38]

Further, in order to form a surface layer for imparting releasability on this photosensitive layer, a resin (P
-39) A solution of 13 g, phthalic anhydride 0.2 g, o-chlorophenol 0.002 g and toluene 100 g was applied using a wire round rod to a film thickness of 1 μm, and after touch-drying, further at 120 ° C. Heated for hours. The adhesive force on the surface of the obtained photoreceptor was 5 g · f.

[0302]

[Chemical Formula 39]

The surface potential of this photosensitive material was +500 V in the dark.
On the photoconductor, except that it was exposed to light of 633 nm with a He-Ne laser so that the exposure amount on the plate surface would be 30 erg / cm ² after being charged. A color toner image was formed. Then, the same operation as in Example 1 was performed to form a full-color image on coated paper. The obtained copy paper showed good performance as in Example 1.

Example 40 100 g of photoconductive zinc oxide, a binder resin (B-4) having the following structure
A mixture of 15 g, 5 g of a binder resin (B-5) having the following structure, 2 g of the resin (P-28), 0.01 g of the dye (D-2) having the following structure, 0.1 g of salicylic acid and 150 g of toluene was put in a ball mill for 2 hours. It was dispersed to obtain a photosensitive layer dispersion liquid.

[0305]

[Chemical 40]

Then, this dispersion was applied onto a 0.2 mm thick base paper for a master for a printing plate, which had been subjected to a conductive treatment and a solvent resistance treatment, with a wire bar, and was dried by touch with a finger, and then in a 110 ° C. circulation type oven for 20 seconds. Heated. Further, it was allowed to stand for 24 hours in the dark under the condition of (25 ° C., 65% RH). The adhesive force on the surface of the photoconductor was 8 g · f.

Next, after corona-charging this photosensitive member to -600 V in a dark place, the same digital image data as in Example 1 was used. First, based on the information about yellow, this time in the positive mirror image mode, Exposure was carried out using a semiconductor laser with light of 780 nm so that the plate surface exposure amount was 25 erg / cm ² . The residual potential of the exposed portion was -120V. Then Versatec 3
A yellow toner for 000 (Xerox color electrostatic blotter) diluted with 50 times Isopar H (made by Esso Standard Petroleum) is used, and a -200V bias is applied to the photoconductor surface side electrode in a developing device having a pair of flat plate developing electrodes. A voltage was applied to perform positive development so that the toner was electrodeposited on the unexposed area, and then rinsed in a bath of Isopar H alone to remove stains on the non-image area. The above process was repeated for each color of magenta, cyan and black. Subsequently, a transfer layer was formed by the same operation as in Example 1, and the transfer layer was transferred to the primary receptor and further to coated paper to form a color image on the coated paper. The obtained color image was a copy having a clear image quality without background fog, and the strength of the image area was sufficient.

Examples 41 to 60 In the same manner as in Example 1, except that 0.3 g of the resin (P-1) was replaced with each resin and / (P) or resin particles (L) shown in Table Q below. Each light-sensitive material was prepared in the same manner as in 1.

[0309]

[Table 27]

Next, these light-sensitive materials were operated in the dark in the same manner as in Example 1 to examine the image pick-up property and transfer property. The obtained color copied images of the coated paper after transfer were clear without background fog, and the image strength was good in durability.

Examples 61 to 71 A mixture of 3.5 g of X-type metal-free phthalocyanine, 10 g of a binder resin (B-6) having the following structure and 80 g of tetrahydrofuran was added.
Put the beads together with glass beads in a 50 ml glass container, disperse for 60 minutes with a paint shaker (manufactured by Toyo Seiki Seisakusho), further add resin (P) or resin particles (L) and a compound for crosslinking shown in the following Table-R for 10 minutes. After the dispersion, the glass beads were filtered to obtain a photosensitive layer dispersion liquid.

[0312]

[Chemical 41]

[0313]

[Table 28]

Then, this dispersion was coated on an aluminum support with a wire bar, dried by touch with a finger, dried in a 110 ° C. circulating oven for 30 seconds, and then heated at 140 ° C. for 1 hour. A transfer image was formed in the same manner as in Example 3 except that this photosensitive member was used instead of the photosensitive member used in Example 3. The obtained color copied image of the coated paper after transfer was clear without background fog, and the image strength was good in durability.

Example 72 A color image was formed on a coated paper in the same manner as in Example 2 except that the means for imparting releasability of the photoconductor was changed to the following contents. Compound (S-3): AW-treated felt [15 mm thick x 20 mm wide wool material] uniformly impregnated with 2 g of dimethyl silicone oil (KF-96L-2.0; manufactured by Shin-Etsu Silicone Co., Ltd.) was used as a photoreceptor. Pressing
Pressed at 200 g, the photosensitive member was rotated at a peripheral speed of 20 mm / sec for 30
It spun for a second. The adhesion of the surface of the photoconductor after processing is 5gf
Became. The final color image obtained showed the same performance as in Example 2.

Example 73 A color image was formed on a coated paper in the same manner as in Example 2 except that the means for imparting releasability of the photoconductor was changed to the following contents. A roller in which a compound (S-4): Fluorosurfactant Surflon (S-141; manufactured by Asahi Glass Co., Ltd.) was wrapped around a rubber roller having a heating means was wound at a surface temperature of 60 ° C. After heating, they were brought into contact with the photoconductor, and both drums were rotated for 30 seconds at a peripheral speed of 20 mm / sec. Adhesive force on the surface of the photoconductor is 12gf
Became. The final color image obtained had the same good results as in Example 2.

Example 74 A color image was formed on a coated paper in the same manner as in Example 2 except that the means for imparting releasability of the photoconductor was changed to the following contents. Silicon rubber roller (made by Kinyo Co., Ltd.) in which silicon rubber is wrapped around a metal core roller
With the surface of the photoconductor at a nip pressure of 500 gf / cm ² and a peripheral speed of 15 m.
It was rotated for 10 seconds at a rotation speed of m / sec. As a result, the adhesive force on the surface of the photoconductor was reduced to 15 g · f. The obtained final color image showed the same performance as that of Example 2.

Examples 75 to 95 In Example 2, instead of the releasable compound (S-1), each compound (S) in the following Table-S was used as a means for imparting the surface releasability of the amorphous silicon photoreceptor. Example 2 except that a solution of a fixed amount in 1 liter of Isopar G was used.
The same operation was performed. By the treatment with each compound (S), the adhesive force on the surface of the photoreceptor was in the range of 3 to 20 g · f. The color image on the obtained coated paper was a good image without fog as in Example 2, and the image strength was also sufficient.

[0319]

[Table 29]

[0320]

[Table 30]

[0321]

[Table 31]

[0322]

[Table 32]

[0323]

[Table 33]

[0324]

[Table 34]

Example 96 5 g of resin particles (AR-4) and resin particles (AR-18) 5 used in the resin (A) dispersion [L-1] of Example 1
A color image was obtained in the same manner as in Example 1 except that 10 g of resin particles (ARW-1) was used instead of g. The final color image obtained showed good performance equivalent to that of Example 1. Further, when the transfer conditions set in Example 1 were set as follows, and a color copy was formed in the same manner, similarly good results were obtained. [Transfer conditions from photoconductor to primary receptor] Photoconductor temperature 60 ° C (no change) Primary receptor temperature 90 ° C Nip pressure 4kgf / cm ² Drum peripheral speed 50mm / sec [Transfer conditions from primary receptor to final transfer material] Primary receptor temperature 60 ° C (no change) Transfer roller 130 ° C (no change) Peeling roller 10 ° C (no change) Nip pressure 3.5kgf / cm ² Drum peripheral speed 50mm / sec Color image obtained under these conditions There was no problem at all. Further, when the transfer was performed under these conditions, no transfer layer remained on the surface of the photoreceptor and the primary receptor after the transfer.

Example 97 In Example 1, instead of the offset printing blanket 9600-A (adhesive force 80 g · f) as the primary receptor, an ethylene / vinyl acetate copolymer (Evaflex 45X; Mitsui. A resin layer made of DuPont Polychemical Co., Ltd. having a film thickness of 10 μm, and a methoxymethyl-modified nylon resin {DAIAMID (DA
IAMID) MX-100; Daicel Huls Ltd.
A resin layer having a film thickness of 1 μm, which is made of a resin, is provided (adhesive force 400 g · f). The compound (S-24)
By dipping 0.5 g in a solution of 1 liter of Isopar H, the surface peelability (adhesive strength 400 g
f) dropped to 105 gf. When a color copy was formed in the same manner as in Example 1 except for above, the same good results as in Example 1 were obtained.

[0327]

According to the present invention, a toner image is formed on a primary receptor having a transfer layer after developing a toner on the surface of a photoreceptor having releasability, and then transferring the entire transfer layer to a transfer material. This makes it possible to easily obtain a high-definition and high-quality glass image. Further, the obtained color copy has excellent storage stability.

Further, a transfer layer is formed on the surface of the primary receptor by a hot melt coating method, an electrodeposition coating method or a transfer method in an apparatus for carrying out an electrophotographic process step and a thermal transfer step to a transferred material. As a result, the primary receptor can be repeatedly used, and a low running cost can be achieved.

Further, it is preferable to adjust the adhesion of the surface of the photoreceptor and the surface of the primary receptor to improve the peeling transferability of the toner image and the transfer layer. Here, the releasing compound (S)
By adsorbing or adhering to the surface of the photoconductor and / or the surface of the primary receptor, the releasability can be imparted to the surface of the photoconductor and / or the primary receptor to adjust the adhesive force. Further, by forming the transfer layer by containing the compound (S) in the electrodeposition dispersion liquid in the electrodeposition coating method, the adhesion of the primary receptor surface and the transfer layer can be formed at the same time.

[Brief description of drawings]

FIG. 1 is a schematic diagram for explaining the method of the present invention.

[FIG. 2] A drum system is adopted as a primary receptor,
It is a figure which shows the example of an apparatus for implementing the method of this invention.

FIG. 3 is a diagram showing an example of an apparatus for carrying out the method of the present invention, which adopts an endless system as a primary receptor.

FIG. 4 is a diagram showing an example of a partial device for forming a transfer layer on a primary receptor using release paper.

FIG. 5 is a diagram showing an example of a device showing an example for depositing a compound (S).

[Explanation of symbols]

1 Support for Photosensitive Member 2 Photosensitive Layer 3 Toner Image 10 Compound (S) Coating Device 11 Photosensitive Member 14 Liquid Developing Unit Set 14Y Yellow Liquid Developing Unit 14M Magenta Liquid Developing Unit 14C Cyan Liquid Developing Unit 14k Black Liquid Developing Unit 15 Intake / Exhaust Unit 15a Intake part 15b Exhaust part 16 Preheating means 17 Temperature adjusting means 18 Corona charging device 19 Exposure device 20 Primary receptor 21 Transfer layer forming device 22 Transfer layer 24 Release paper 25a Preheating means 25b Heating roller 25c Cooling roller 30 Transfer material 31 Transfer Backup roller 32 Backup roller for peeling 110 Compound (S) coating portion 111 Transfer roll 112 Metalling roll 113 Compound (S) 120 Transfer to primary receptor using release paper Transfer moiety to the layer forming part 130 transfer material

Claims (8)

[Claims] 1. A toner image of one or more colors is formed on an electrophotographic photosensitive member having a releasable surface by an electrophotographic process, and the toner image is transferred onto a primary receptor provided with a releasable transfer layer. A method for forming a color image, wherein the toner image on the primary receptor is transferred together with a transfer layer onto a final transfer material. 2. The color image forming method according to claim 1, wherein the peelable transfer layer is formed by at least one of a hot melt coating method, an electrodeposition coating method and a transfer method. 3. The surface of the electrophotographic photosensitive member is JIS Z0237-19.
80. The adhesive force according to 80 “adhesive tape / adhesive sheet test method” is 100 gram · force or less, and the adhesive force of the surface of the primary receptor is larger than the adhesive force of the surface of the photoconductor. 2. The color image forming method as described in 2. 4. The color image according to claim 3, wherein a compound (S) containing at least a fluorine atom and / or a silicon atom is adsorbed or attached to the surface of the electrophotographic photosensitive member to form a peelable surface. Forming method. 5. The color image forming method according to claim 3, wherein a compound (S) containing at least a fluorine atom and / or a silicon atom is adsorbed or attached to the surface of the primary receptor. 6. The peelable transfer layer has a relative dielectric constant of 3.5.
The following electrically insulating organic solvent contains at least one compound (S) containing at least 0.01 g of a fluorine atom and / or a silicon atom dissolved in 1.0 liter of the organic solvent, and has a glass transition point. It is formed by using an electrodeposition dispersion liquid in which resin particles (AR) having a softening point of 140 ° C. or less or a softening point of 180 ° C. or less are dispersed to deposit the resin particles (AR) by electrophoresis to form a film. 5. The color image forming method according to claim 3 or 4. 7. A means for forming a toner image of at least one color on an electrophotographic photoreceptor having a releasable surface by an electrophotographic process, a means for providing a releasable transfer layer on a primary receptor, the toner on the primary receptor. A color image forming apparatus comprising at least a means for transferring an image and a means for transferring the toner image together with a transfer layer from a primary receptor to a final transfer material. 8. A means for supplying a compound (S) containing at least a fluorine atom and / or a silicon atom to the surface of an electrophotographic photosensitive member and / or a primary receptor, and at least one color on the electrophotographic photosensitive member by an electrophotographic process. Of forming a toner image, means for providing a releasable transfer layer on the primary receptor, means for transferring the toner image on the primary receptor, and transfer of the toner image from the primary receptor to the final transfer material together with the transfer layer A color image forming apparatus comprising at least a means.